Method for tuning product composition based on varying types and ratios of feed

ABSTRACT

A process of tuning a hydrocarbon product composition is described. The process involves selecting paraffins for reaction. The equilibrium constants for reactions of the selected paraffins can be used to select appropriate feed ratios, or an equilibrium composition as function of C/H molar ratio. A selected feed is reacted to obtain the product. Equilibrium product compositions and non-equilibrium product compositions can be obtained using the process.

BACKGROUND OF THE INVENTION

The Reid vapor pressure (RVP) of gasoline has been utilized by theEnvironmental Protection Agency as a means of regulating volatileorganic compounds emissions by transportation fuels and for controllingthe formation of ground level ozone. As these regulations become morestringent and as more ethanol (which has a high vapor pressure) isblended into gasoline. C₅ paraffins need to be removed from the gasolinepool. Moreover, the need to remove components may also extend to some C₆paraffins. This may result in refiners being oversupplied with C₅paraffins and possibly C₆ paraffins.

Disproportionation reactions offer a possible solution to this problem.The disproportionation of paraffins (e.g., isopentane (iC₅)) involvesreacting two moles of hydrocarbon to form one mole each of two differentproducts, one having a carbon count greater than the starting materialand the other having a carbon count less than the starting material asshown in FIG. 1. The total number of moles in the system remains thesame throughout the process, but the products have different carboncounts from the reactants. Additional secondary disproportionation-typereactions can occur in which two hydrocarbons having different carbonnumbers react to form two different hydrocarbons having different carbonnumbers form those of the feed where the total number of carbons in theproducts does not change from the total number in the feed (e.g.,pentane and octane reacting to form hexane and heptane).

There are a number of different catalysts that have been shown toproduce the desired paraffin disproportionation reaction, includingzeolites, sulfated zirconias, AlCl₂/SiO₂, ionic solids, platinum onchlorided Al₂O₃/Ga₂O₃ supports, supported ionic liquids. Pt/W/Al₂O₃ andHF/TiF₄. However, these processes have a number of disadvantages. Theprocesses using zeolites, sulfated zirconias, AlCl₂/SiO₂, ionic solids,and platinum on Al₂O₃/Ga₂O₃ supports require elevated temperatures(e.g., 120-450° C.) to carry out the transformation. The HF/TiF₄ systemis capable of disproportionation at 51° C. but it utilizes dangerous HF.The supported ionic liquid is active from about 85-125° C. and iscomposed of the Brønsted acidic trimethylammonium cation. Since theionic liquid's organic cation is composed of this Brønsted acid, theacid concentration within this catalyst is stoichiometric with respectto the ionic liquid and quite high. Moreover, the supported ionic liquidis deactivated by leaching of the ionic liquid from the support.Additionally, the use of a support increases the cost of the catalystand may result in a chemical reaction of the support with the acidicionic liquid over time, as happens when AlCl₃ is immobilized on silica.

Isomerization processes have been used to improve the low octane numbers(RON) of light straight run naphtha. Isomerization processes involvereacting one mole of a hydrocarbon (e.g., normal pentane) to form onemole of an isomer of that specific hydrocarbon (e.g. isopentane), asshown in FIG. 2. The total number of moles remains the same throughoutthis process, and the product has the same number of carbons as thereactant.

Current isomerization processes use chlorided alumina, sulfatedzirconia, or zeolites in conjunction with platinum. Process temperaturesrange from about 120° C. for chlorided alumina up to about 260° C. forzeolite type catalysts. These reactions are run at temperatures whichallow the feed to reach equilibrium. At lower temperatures, theequilibrium favors the branched isomers possessing the higher octanenumber.

Isomerization processes utilizing ionic liquids have been developed. Forexample, US 2003/019767 describes an isomerization process for aparaffin hydrocarbon feed using an ionic liquid as a catalyst. The ionicliquid is formed from an N-containing heterocyclic and/or N-containingaliphatic organic cation and an inorganic anion derived from metalhalides. The examples show a catalyst:hydrocarbon weight ratio of 1:1 or1.5:1. The hydrocarbon feeds examined were normal pentane, normalheptane, normal octane, and 3-methylhexane.

US 2004/059173 teaches an isomerization process for linear and/orbranched paraffin hydrocarbons. The catalyst comprises an ionic liquid.Over 25 wt. % of a cyclic hydrocarbon additive is included. The ionicliquid is formed from an N-containing heterocyclic and/or N-containingaliphatic organic cation and an inorganic anion derived from metalhalides. The ionic liquid:hydrocarbon ratio in the examples is fixed at1:1 volume ratio. Metal salt additives or Brønsted acids can beincluded. The feed is a mixture of C₇ hydrocarbons.

U.S. Pat. No. 7,053,261 discusses isomerization of linear and/orbranched paraffin hydrocarbons using an ionic liquid catalyst incombination with a metal salt additive. The ionic liquid is formed froman N-containing heterocyclic and/or N-containing aliphatic organiccation and an inorganic anion derived from metal halides. The ionicliquid:hydrocarbon ratio in the examples is fixed at 1:1 volume ratio.The results of the gas chromatograph on the paraffin phase were notreported. The feed is a mixture of C₇ hydrocarbons.

All of these references describe isomerization of the feed; nonedescribes disproportionation reactions. All of the references describethe use of ionic liquids having an acid concentration of at least about3.0 M. The Brønsted acidic ionic liquid used in US Publication2003/0109767 was [trimethylammonium][Al₂Cl₇], which has a molarconcentration of HCl that ranges from 3.0-4.1 M if the density is in therange of 1.1 to 1.5 g/mL. For US Publications 2004/0059173 and U.S. Pat.No. 7,053,261 the Brønsted acidic ionic liquid used was[trimethylammonium][Al_(1.8)Cl_(6.4)], which has a molar concentrationof HCl that ranges from 3.3-4.5 M if the density is in the range of 1.1to 1.5 g/mL. These estimated densities are within the ranges measuredfor similar ionic liquids.

None of the references indicate the composition of the product mixture:as a result, it is unclear what was actually formed in the reactions.Assuming that all of the other products were disproportionation products(which is unlikely to be correct as Ibragimov et al. teach that crackingoccurs in addition to disproportionation (see below), but it sets anupper limit on the greatest possible conversion, yield, etc. for thedisproportionation products). The conversion rates corrected for mass orvolume were calculated as follows: using the reported iso-selectivity,the selectivity to other compounds was calculated as(100-iso-selectivity). The % conversion was determined from the reported%-iso yield and % iso-selectivity. The % conversion thus determined wasused to determine the reaction rate by the following formula: volumerate=(% conversion/time (h))×(mL HC/mL IL) or as mass rate=(%conversion/time (h))×(g HC/g IL). The % conversion was then used withthe computed selectivity to other compounds to set an upper limit on theyield of disproportionation products. The yield of the other compoundsand yield of isomers was then calculated using the calculatedselectivity to other compounds and the total yield. Since the reactionrate is dependent on the ratio of ionic liquid:hydrocarbon, the rateswere corrected according to these ratios.

With respect to US 2003/0109767, the corrected conversion rates for masswere very low. For n-C₅, the corrected conversion rate for mass rangedwas between 3.5 and 18.2. For n-C₇, it ranged from 2.6 to 9.3, for n-C₈,it was 3.3, and for 3-methylhexane, it was 4.7. For US 2005/059173, thecorrected conversion rates for volume ranged from 0.6 to 47.1 for the C₇mixture. For U.S. Pat. No. 7,053,261, the corrected conversion rates forvolume ranged from 5.4 to 371.3 in the presence of an additional metalsalt.

Isomerization is also described in “Isomerization of Light AlkanesCatalysed by Ionic Liquids: An Analysis of Process Parameters,”Ibragimov et al., Theoretical Foundations of Chemical Engineering(2013), 47(1), 66-70. The desired reaction is stated to beisomerization, and the main isomerization products from n-hexane aresaid to isobutane, isopentane, and hexane isomers. However, isobutaneand isopentane are not the isomerization products of n-hexane asisomerization has been defined above. In addition, the article discussesthe fact that a significant amount of an undesirable disproportionationreaction begins to occur after about 2-3 hrs. The article indicates thatthe disproportionation reaction dominates when the ratio of catalyst tohydrocarbon ratio is 2:1, and that cracking and disproportionationdominate at 333K. Because cracking is occurring, the number of molesformed is increased. The optimum isomerization temperature was 303K. Themaximum volume rate they obtained was 26 at their high mixing speeds(900 rpm or more) at 0.5 hr.

Some processes involve isomerization and then a cracking reaction inwhich one mole of a hydrocarbon forms two moles of product, each with alower carbon number than the starting material. In FIG. 3, the productsare illustrated as an alkene and an alkane. Additionally, the totalnumber of moles increases throughout the process.

Alkylation processes involving ionic liquids are also known. Inalkylation reactions, one mole of an alkane and one mole of an alkenereact to form one mole of an alkane having a carbon number equal to thesum of the carbon numbers of the starting alkane and alkene, as shown inFIG. 4. In an alkylation process, the total number of moles in thesystem is reduced.

There is a need for methods of controlling the product feeds to obtaindesired product compositions.

SUMMARY OF THE INVENTION

One aspect of the invention is a process of tuning a hydrocarbon productcomposition. In one embodiment, the process includes selecting a rangeof paraffins, and determining a series of equilibrium constants forreactions of the selected range of paraffins. A desired productcomposition is selected based on an equilibrium composition. Ahydrocarbon feed is selected based on the desired product composition,the selected hydrocarbon feed comprising at least one C_(n) alkane wheren=1-200. A feed ratio is determined based on the selected hydrocarbonfeed and the desired product composition. The selected hydrocarbon feedis reacted by contacting the selected hydrocarbon feed with a liquidcatalyst in the determined feed ratio in a reaction zone under tuningconditions to form the desired product composition, the liquid catalystcomprising an ionic liquid and a carbocation promoter, and the desiredproduct composition is recovered.

Another aspect of the invention relates to a process of tuning ahydrocarbon product composition. In one embodiment, the process involvesselecting a range of paraffins, and determining a series of equilibriumconstants for reactions of the selected range of paraffins. Anequilibrium composition of the selected range of paraffins as a functionof C/H molar ratio is determined. A hydrocarbon feed to react isselected, the selected hydrocarbon feed comprising at least one C_(n)alkane where n=1-200. The selected hydrocarbon feed is reacted bycontacting the selected hydrocarbon feed with a liquid catalyst in areaction zone under tuning conditions to form the product composition,the liquid catalyst comprising an ionic liquid and a carbocationpromoter.

In one embodiment, an equilibrium composition is obtained. A desiredequilibrium product composition is selected from the equilibriumcomposition corresponding to a selected C/H molar ratio. The hydrocarbonfeed is selected based on the desired equilibrium product composition,and the C/H molar ratio of the selected hydrocarbon feed matches theselected C/H molar ratio of the desired equilibrium product composition.The selected hydrocarbon feed is reacted to form the desiredsubstantially equilibrium product composition, and the desiredsubstantially equilibrium product composition is recovered.

In another embodiment, a non-equilibrium composition is obtained. TheC/H molar ratio of the selected hydrocarbon feed is determined, and theequilibrium composition at the C/H molar ratio for the selectedhydrocarbon feed is determined. The selected hydrocarbon feed is reactedto form a desired non-equilibrium product composition, and the desirednon-equilibrium product composition is recovered.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the disproportionation reaction of iso-pentane.

FIG. 2 illustrates the isomerization reaction of n-pentane.

FIG. 3 illustrates a cracking reaction of n-pentane.

FIG. 4 illustrates an alkylation reaction of isobutane and isobutene.

FIG. 5 is a schematic of one embodiment of the process of presentinvention.

FIG. 6 is a schematic of one embodiment of the process of presentinvention.

FIG. 7 is graph showing the concentration of components in adisproportionation reaction mixture of isopentane over time.

FIG. 8 is a graph showing the weight of C₅₊ products and RON at variousfeed ratios of 2-methylpentane/isobutane if the reaction were to be runto equilibrium and were to include only isopentane, 2-methylpentane andisobutane as the components present.

FIG. 9 is a graph of the equilibrium composition (in mole %) of C₄ to C₈paraffins as a function of the C/H ratio at 100° C.

FIG. 10 is a graph comparing the calculated equilibrium composition (inmole %) of C₄ to C₈ paraffins as a function of the C/H ratio at 100° C.compared to the experimental data on the mole % distribution of the C4+fraction.

DETAILED DESCRIPTION OF THE INVENTION

Paraffins have a wide range of properties which makes some paraffinisomers more valuable than others. For example, isobutane has an RON of100 and an RVP of 71 psi, while normal pentane has an RON of 62, and anRVP of 15.6 psi. This dramatic difference in properties leads todifferences in refiners' valuation of various products depending ontheir location, the source of crude oil, and their desired productspecifications. Constantly changing product demands sometimes result intoo much of a less desirable product and too little of a more desirableone, resulting in increased prices for the more desired product.Furthermore, an excess of a particular feed can lead to a lower pricefor that feed.

It would be desirable to have a process that allows a refiner to selecta particular desired product preferentially, such as gasoline, diesel,kerosene, or some other paraffin containing product, depending on themarket situation at a particular time and to shift easily from oneproduct to another as the demand changes. In addition, it would bedesirable to be able to select the feed used in the process to produce adesired product based on the available supply of possible feeds,allowing maximization of the use of lower price feeds. The productcomposition can be tuned by varying the types and amounts of differentfeeds. The process utilizes one or more of disproportionation, reversedisproportionation, and isomerization of the selected feed to form thedesired product.

It has been demonstrated that an acidic ionic liquid and a carbocationpromoter can catalyze the disproportionation of paraffins, as discussedbelow. In this reaction, two moles of a paraffin are used to create onemole each of two different paraffins one larger in carbon count and onesmaller than the starting paraffin. For example, pentane can beconverted to a product mixture containing butane and hexane.

Reverse disproportionation involves the microscopic reverse of thedisproportionation reaction, for example, in which one mole of hexaneand one mole of butane react to form two moles of pentane. Utilizing theequilibrium among the various species, the concentration of the productcan be controlled by varying the relative ratios of the species.Consequently, two different paraffinic feed sources of varying carboncount can be reacted to obtain a product of intermediate carbon count.

More generally, this process involves the net transfer of CH₂ unitsbetween paraffins, where CH₂ unit refers to the transfer of 1 C and 2 H,not necessarily a methylene unit. The products result from the donationand acceptance of net CH₂ units to and from various paraffins. Thus, twoparaffinic feeds having different carbon counts can be reacted toproduce a product having an intermediate carbon count. For example, thereaction of butane with a larger paraffin, e.g., C₆, produces a productcontaining paraffins in the C₅ to C₁₅ range.

In addition to the net CH₂ transfer, the process favors the formation ofbranched paraffins, which are more valuable than normal paraffinsbecause they have more desirable octane numbers and cloud points.

The Gibbs free energy for these types of reactions is relatively small.Consequently, the equilibrium constants for these reactions are notsubstantially large or small for any given reaction. Due to these modestequilibrium constants, at equilibrium measurable amounts of bothreactant and product will be formed. As shown in FIG. 7, an equilibriumappears to have been reached among butanes, pentanes, hexanes and C₇₊paraffins in the disproportionation reaction of isopentane. Theestimated equilibrium constant for the specific disproportionationreaction of two moles of isopentane to one mole of isobutane and onemole of 2-methylpentane is Keq=0.3 based on the enthalpy of formationand the molar entropy for the reactants and products. The value observedby gas chromatography was 0.4, which is in good agreement with thecalculated value. Furthermore, the ratio of the products did not changeas the reaction time was increased.

The general formula for a paraffin is C_(n)H_(2n+2). For any givenparaffin, it can be represented by a C/H molar ratio. For example. C/Hmolar ratio for both isobutane and normal butane is 0.400, while theratio for isopentane and normal pentane is about 0.417. Blends of two ormore paraffins can produce C/H molar ratios in the range of about 0.25to about 0.50.

For a given C/H molar ratio, there exists a specific equilibriummixture. For a given subset of paraffins, there exists a definedequilibrium composition at a given C/H molar ratio. If this subset ischosen such that it encompasses the majority of the measurable products,then this equilibrium composition for this subset of paraffins can beused to approximate the composition of the product at the end of areaction, provided a catalyst could be identified to carry out thisequilibration for these paraffins. At the specified C/H molar ratio, ifa compound is present in excess of its equilibrium concentration, thenit will be consumed. Conversely, if a compound is present at less thanits equilibrium concentration, it will be produced. By appropriateselection of feeds, desired compounds can be produced, and undesiredcompounds can be consumed.

As illustrated in Table A, Feeds 1 and 2 have the same C/H molar ratio,0.406, but they have different starting compositions. Both feeds willproduce the same product composition. With Feed 1, the amounts of the C₄and C₇ paraffins are in excess of the equilibrium amounts, and so bothwill be consumed to produce the equilibrium mixture. With Feed 2, theamount of C₅ paraffin is in excess of the equilibrium amount, so it willbe consumed, while the amount of C₄ paraffin is less the equilibriumamount, so it will be produced.

TABLE A Compound Feed 1(mole %) Feed 2 (mole %) Product (mole %) C4P 9070 76.5 C5P 0 30 17.9 C6P 0 0 4.7 C7P 10 0 0.8 C8P 0 0 0.1 C/H 0.4060.406 0.406

FIG. 9 shows a graph of the equilibrium composition (in mole %) of asubset of paraffins (C₄ to C₈ paraffins) as a function of the C/H molarratio. The equilibrium constants for all of the reactions (isomerizationand disproportionation) were determined using values for an ideal gas at100° C. from “The Chemical Thermodynamics of Organic Compounds” byDaniel R Stull, Edgar F. Westrum, Jr. and Gerard C. Sinke, copyright1969. As demonstrated in FIG. 9, the equilibrium product composition isa function of C/H ratio of the feed. The composition listed is for asubset of paraffins; the figure can be extended to include paraffinslarger than C₈ and smaller than C₄, if desired. These productcompositions represent the equilibrium composition for specific C/Hmolar ratios of this subset of paraffins, provided a catalyst can beidentified to carry out these reactions. Once a catalyst has beenidentified that is capable of catalyzing these reactions, the productcomposition will eventually yield the equilibrium composition as set bythe C/H molar ratio. Suitable catalysts include those capable ofcatalyzing paraffin disproportionation, reverse disproportionation,metathesis, alkylation and isomerization reactions. Suitable reactiontimes are less than about two days, or less than about one day, or lessthan about 18 h, or less than about 12 h, or less than about 6 h, orless than about 5 h, or less than about 4 h, or less than about 3 h, orless than about 2 h, or less than about 1 h. The use of the catalyst inconjunction with the known equilibrium composition based on the molarC/H ratio then allows for selective production and consumption ofspecific paraffins. For instance, if a refiner had an excess of butanesand wished to react these away, the refiner would identify an acceptableequilibrium product composition based on the C/H molar ratio, and thenreact the butanes with a suitable paraffin such that the predeterminedC/H molar ratio would be achieved. In this manner, the undesired butaneswould be upgraded and produce the predetermined acceptable productcomposition.

FIG. 10 shows a graph comparing the calculated equilibrium productcomposition (in mole %) of C₄ to C₈ paraffins as a function of the C/Hmolar ratio to the mole % distribution of the C4+ fraction inexperimental data. The graph shows very good agreement between thepredicted value and the experimental data. The experimental dataincluded in FIG. 10 are from Examples 10, 17, 18, 22, 26, 27, 30, 32,33, 35-37.

Thus, a refiner can select a desired product composition from the figure(or a corresponding graph including the appropriate paraffins), anddetermine the C/H molar ratio corresponding to that desired productcomposition. The refiner may then choose one or more low valued feedstreams to achieve the C/H molar ratio necessary to obtain the desiredcalculated equilibrium product composition. In this approach, theproduct composition is independent of the composition of the feed sinceit is reacted to equilibrium and the product composition will be knownbeforehand. Alternatively, a refiner may use the same figure to obtain adesired product composition that is significantly different from theequilibrium composition by choosing a feed that is not at itsequilibrium composition and reacting for a period of time shorter thanthat required to reach equilibrium. In this approach, the refiner wouldbe targeting the initial products formed from the starting material: inthis approach, the product composition may be dependent on thecomposition of the feed.

Although this is a simplified system, an equilibrium constant exists forany combination of paraffins. Once the constants are known, the feedratios required obtaining specific compositions of one or more desiredproducts can be determined. By selecting the appropriate feedcompositions and feed ratios, various product compositions can beobtained.

The reaction can be allowed to proceed to form an equilibrium (orsubstantially equilibrium) product composition, as described above. By“substantially equilibrium product composition.” we mean that theproduct composition contains 95 wt % or more of the equilibrium productcomposition for at least one component as determined by the C/H ratio,or 95 wt % or more of the equilibrium product composition for at leasttwo components, or 95 wt % or more of the equilibrium productcomposition for at least three components. When more than one componentis considered, the components have consecutive carbon numbers, e.g., C₄,C₅, and C₆. While a component may have reached equilibrium, it is notrequired that the isomers of the component have reached theirequilibrium. For example, the C₄ component may have reached theequilibrium concentration, but it may not have reached the equilibriumfor normal butane and isobutane.

In other embodiments, there may be a desire for a non-equilibriumproduct composition. By “non-equilibrium product composition,” we meanthat the product composition contains less than 95 wt % of theequilibrium product composition for at least one component as determinedby the C/H ratio, or less than 95 wt % of the equilibrium productcomposition for at least two components, or less than 95 wt % of theequilibrium product composition for at least three components. When morethan one component is considered, the components have consecutive carbonnumbers, e.g., C₄, C₅, and C₆. For example, a product containing aniC4/nC4 ratio greater than the equilibrium amount may be desired. Thepresent process allows the production of such desired non-equilibriumproducts.

After determining the equilibrium composition of the selected range ofparaffins as a function of C/H molar ratio and selecting the hydrocarbonfeed, the C/H molar ratio of the selected hydrocarbon feed isdetermined. The equilibrium composition at the C/H molar ratio for theselected hydrocarbon feed is then determined. The selected hydrocarbonfeed is then reacted to form a desired non-equilibrium productcomposition. The reaction is stopped before the equilibrium productcomposition is reached. The product composition can be monitored todetermine the appropriate stopping point to obtain the desirednon-equilibrium composition. Suitable monitoring methods are known tothose of skill in the art and include, but are not limited to, gaschromatography (GC), gas chromatography mass spectrometry (GC-MS) andGC×GC. The desired non-equilibrium product composition can then berecovered.

The process can be controlled to obtain a certain desired property forthe product composition. For example, desired properties could includeone or more of research octane number, boiling point, boiling range,cloud point, pour point, viscosity, density and Reid vapor pressure. Thehydrocarbon feed would be selected based on the product composition andthe desired property.

In some embodiments, the recovered product is separated into two or moreproduct streams, for example by boiling point. In some embodiments, allor a portion of one or more of the product streams can be recycled backto the reaction zone. The amount of recycle can be adjusted to maintaina desired C/H molar ratio of the hydrocarbon stream entering thereaction zone at a particular value.

The ionic liquid can be separated from the product, and recycled to thereaction zone. The used ionic liquid can be regenerated before beingrecycled to the reaction zone as needed.

In some embodiments, the C/H molar ratio of the selected hydrocarbonfeed is in the range of about 0.25 to about 0.50, or about 0.30 to about0.50, or about 0.40 to about 0.50, or about 0.40 to about 0.49, or about0.40 to about 0.48, or about 0.40 to about 0.47, or about 0.40 to about0.46, or about 0.40 to about 0.45, or about 0.40 to about 0.44, or about0.40 to about 0.43, or about 0.40 to about 0.42, or about 0.40 to about0.41.

Typically, hydrocarbons having a carbon number from 1-200 or more can beselected as feeds for the process. Depending on the desired product, oneor two (or more) hydrocarbon feeds could be selected.

In some embodiments involving reverse disproportion, one larger and onesmaller paraffin feed can be used to produce a product compositionhaving an intermediate carbon count. The smaller feed typically hascarbon numbers ranging from 1-198, and the larger feed typically hascarbon numbers ranging from 3-200. There is generally a difference of atleast 2 or more carbon numbers between the two feeds, or at least 3, orat least 4, or at least 5, or at least 6 or more. In some embodimentsinvolving reverse disproportionation, the reaction mixture has an amountof at least one of the intermediate products equal to or in excess ofthe amount formed by the disproportionation reaction of either feedalone.

By the appropriate selection and reaction of hydrocarbon feeds, productsof a desired composition can be obtained. This could allow the use ofreadily available but lesser valued feeds to produce more valuableproducts.

For example, the production of natural gas liquids, which includesbutanes, is rapidly increasing. As a result of this increase, the priceof butanes could be significantly reduced, creating a burden forproducers. Only a small fraction of butanes can be included in thegasoline pool because of its high vapor pressure. Reversedisproportionation offers a possible solution. The reaction of butaneswith a larger paraffin, e.g., C₁₂, can produce a product mixturecontaining paraffins in the C₅ to C₁₁ range gasoline range, as well assome C³⁻ and C₁₃₊ paraffins.

Other highly desirable products include kerosene, which is widely usedfor jet fuel, and diesel, the demand for which currently exceeds that ofgasoline. They are currently obtained by the distillation of crude oiland hydrocracking of heavier feeds. Therefore, a process which convertslow value paraffins into kerosene or diesel would be very beneficial. Asan example, the reaction of a gasoline range paraffin, such as C₉, witha larger paraffin, such as C₁₆, can produce a product mixture in the C₁₀to C₁₅ range, as well as some C⁸⁻ and C₁₇₊ paraffins. In a like manner,the reaction a gasoline range paraffin, such as C₉, with a much largerparaffin, such as C₂₅, can produce a product mixture in the C₁₀ to C₂₄range, as well as some C⁸⁻ and C₂₆₊ paraffins.

Light paraffins and methane are difficult compounds to react; as aresult, they can be a source of wasted carbon in a refinery. Because oftheir low reactivity and high vapor pressure, the utility of thecompounds is limited. For example, only small amounts of these compoundscan be blended into gasoline. As the production of shale gas and shalecrude continues, these light paraffins and methane will be produced onan even larger scale, which will depress their value further.

Methane can be reacted with C₃₊ paraffins to form a mixture of C₂₊paraffins. For example, methane could be reacted with propane to form C₂paraffin. Methane could be reacted with butane to form a mixture of C₂and C₃ paraffins. Methane could be reacted with pentane to form amixture of C₂ to C₄ paraffins. Methane could be reacted with a lightnaphtha stream (C₅ to C₆ paraffins) to form a mixture of C₂ to C₄₋₅paraffins. Methane could be reacted with a heavy naphtha stream (C₇ toC₁₂ paraffins) to form a mixture of C₂ to C₁₁ paraffins. Methane couldbe reacted with a heavy paraffin stream (C₁₂₊ paraffins) to form amixture of C₂ to C₁₁₊ paraffins.

Ethane can be reacted with C₄₊ paraffins to form a mixture of C₃₊paraffins. For example, ethane could be reacted with butane to form C₃paraffins. Ethane could be reacted with pentane to form a mixture of C₃to C₄ paraffins. Ethane could be reacted with a light naphtha stream (C₅to C₆ paraffins) to form a mixture of C₃ to C₄₋₅ paraffins. Ethane couldbe reacted with a heavy naphtha stream (C₇ to C₁₂ paraffins) to form amixture of C₃ to C₁₀, paraffins. Ethane could be reacted with a heavyparaffin stream (C₂₊ paraffins) to form a mixture of C₃ to C₁₁paraffins.

Propane can be reacted with C₅₊ paraffins to form a mixture of C₄₊paraffins. For example, propane could be reacted with pentane to form C₄paraffins. Propane could be reacted with a light naphtha stream (C₅ toC₆ paraffins) to form a mixture of C₄ to C₅ paraffins. Propane could bereacted with a heavy naphtha stream (C₇ to C₁₂ paraffins) to form amixture of C₄ to C₁₁₊ paraffins. Propane could be reacted with a heavyparaffin stream (C₁₂₊ paraffins) to form a mixture of C₄ to C₁₁₊paraffins.

Butane can be reacted with C₆₊ paraffins to form a mixture of C₅₊paraffins. For example, butane could be reacted with a light naphthastream (C₅ to C₆ paraffins) to form a mixture of C₅ paraffins. Butanecould be reacted with a heavy naphtha stream (C₇ to C₁₂ paraffins) toform a mixture of C₅ to C₁₁ paraffins. Butane could be reacted with aheavy paraffin stream (C₁₂₊ paraffins) to form a mixture of C₅ to C₁₁₊paraffins.

One of the problems with renewable diesel fuel (about C₁₆) is that thefeed for the process is limited and cannot meet current demand.Providing a route allowing more fuel to be produced from the diesel feedcould be valuable. The present invention provides a method of increasingthe fuel volume of the renewable diesel feed to C₅₊ paraffins, which arecomponents in gasoline. This can be accomplished by reacting therenewable diesel feed with one or more of methane, ethane, propane, orbutane to form C₅₊ paraffins at low temperatures and pressures.Alternatively, the renewable diesel feed could be reacted with a lightparaffin stream, e.g., a C₃ to C₆ stream, to form a mixture of C₅₊paraffins. The fuel volume increases because the butanes (or methane,ethane, and/or propane) are incorporated into the C₅₊ paraffins,resulting in an increase in the mass of the C₅₊ fraction and a decreasein product density compared to the renewable diesel feed.

Another area where the present process can be used involves products ofthe Fischer-Tropsch process, which converts syngas (H₂/CO) into ahydrocarbon mixture, ideally in the diesel range. However, the processproduces a large range of components, including Fischer-Tropsch wax,which are large paraffins (e.g., in the range of about 18 to 200 or morecarbons) that are solid at room temperature and are undesirable.Typically, these compounds are hydrocracked to smaller fragments. Theseheavy compounds can be reacted with lighter paraffins, such as methane,ethane, propane, butane, or pentane, to produce a mixture of productshaving intermediate molecular weight, e.g., C₅₊ paraffins. The mass ofthe C₅₊ paraffins product is greater than the mass of theFischer-Tropsch wax feed, and it has a density less than the density ofthe Fischer-Tropsch wax feed.

In some embodiments, the amount of C₁, C₂ and C₃ alkanes produced in thereaction may be very small. As a result, in some embodiments, theseproducts may be ignored. Additionally, the maximal concentration of theC_(n+1) and C_(m-1) type compounds is set by the C/H molar ratio in thefeed which may not allow for a high concentration of some species. Forexample, in some reactions that employ heavy paraffins (e.g. hexadecane)blended with smaller paraffins (e.g. butane), the amount of alkanesproduced in the C₁₅ (C_(m-1)) region may be very small because thethermodynamic concentration of these species at the feed's total C/Hmolar ratio may be very small. As a result, in some embodiments, theseproducts may be ignored.

Thus, reverse disproportionating two feeds where the first comprisesC_(n) and the second comprises C_(m) will produce at least one productC_(z) where n<z<m. There will typically be a range of products withinthe range: however, the amounts of some may be so small that they arenot considered. For example, depending on the C/H ratio, reversedisproportionating two feeds where the first comprises C₁₋₄ and thesecond comprises C₅₋₁₂ will produce at least one product in the C₂₋₁₁range. In some embodiments, the amounts of some of the products in thatrange may be so small as to be ignored. Similarly, reversedisproportionating C₁₋₉ and C₆₋₁₆ feeds will produce at least oneproduct in the C₂₋₁₅ range. The amounts of some of those products may beso small as to be ignored. Reverse disproportionating C₁₋₁₀ and C₆₋₂₅feeds will produce products in the C₂₋₂₄ range. The amounts of someproducts in the range may be so small as to be ignored. Reversedisproportionating C₁₋₂₃ and C₆₋₁₀₀ feeds will produce products in theC₂₋₉₉ range. The amounts of some of the products may be so small as tobe ignored.

This process has a number of important advantages. The productcomposition would be tunable based on the ratio and compositions of thefeeds. It is a low temperature, low pressure process. It uses ionicliquids that have similar acidity to those used in the alkylationprocess. It can be used to produce gasoline from butanes, and keroseneand diesel from gasoline. The reaction products are primarilyisoparaffins, which would be beneficial for cloud point and octane.

Reactions involved in the tuning process include disproportionation,isomerization, and reverse disproportionation reactions. Reversedisproportionation feeds and reaction conditions are similar to thosediscussed below for isomerization and disproportionation reactions.

Disproportionation and/or isomerization of a hydrocarbon feed using aliquid catalyst comprising ionic liquids and carbocation promoters isdescribed. The ionic liquids can be supported or unsupported and allowthe reactions to occur at temperatures below about 200° C.

The disproportionation reaction involves contacting a hydrocarbon feedcomprising a C_(n) alkane with a liquid catalyst in a reaction zone toform a product mixture containing C_(n−) alkanes and C_(n+) alkanes. Theliquid catalyst comprises an ionic liquid and a carbocation promoter,and n=2-200.

The isomerization reaction involves contacting the hydrocarbon feedcomprising a normal C_(n) alkane (or iso C_(n) alkane) with a liquidcatalyst in a reaction zone to form a product mixture containing isoC_(n) alkanes (or normal C_(n) alkanes). The liquid catalyst comprisesan ionic liquid and a carbocation promoter, and wherein n=4-200.

Disproportionation and isomerization occur simultaneously. There is asubstantial disproportionation reaction, which can be seen by the factthat significant amounts of C_(n+) and C_(n−) alkanes form. The productmixture can contain at least about 3 wt % C_(n+) alkanes in 1 hr basedon the C_(n) alkane fraction in the hydrocarbon feed, or at least 5 wt%, or at least about 7 wt %, or at least about 10%, or at least about 15wt %, or at least about 20 wt %. There is a corresponding formation ofthe C_(n−) fraction. There can be at least about 3 wt % C_(n−) alkanesin 1 hr based on the C_(n) alkane fraction in the hydrocarbon feed, orat least 5 wt %, or at least about 7 wt %, or at least about 10%, or atleast about 15 wt %, or at least about 20 wt %. The percentages arebased on the C_(n) alkane fraction in the hydrocarbon feed.

It is more complex to evaluate the C_(n+) and C_(n−) fractions when thefeed comprises more than one C_(n) alkane. When the feed comprises morethan one C_(n) alkane, the amount of C_(n+) alkane based on the highestcarbon number in the feed can be used. For example if, the feedcomprises C₅ and C₆, the amount of C_(n+) can be evaluated using the C₇fraction. When the feed comprises C₅ and C₅, the increase may beevaluated using the C₉ fraction.

For a feed comprising C₅, at least about 5 wt % each of C⁴⁻ and C₆₊forms within 30 min, or at least about 10 wt %, or at least about 15 wt%. At least about 10 wt % each of C⁴⁻ and C₆₊ forms within 1 hr, or atleast about 15 wt %, or at least about 20 wt %.

For a feed comprising C₇, at least about 3 wt % each of C⁶⁻ and C₈₊forms within 1 hr, or at least about 5 wt %, or at least about 7 wt %.

Another indication of the existence of the disproportionation reactionis that the number of moles in the product is nearly equal to the numberof moles initially present.

There can also be a substantial isomerization reaction, which can beseen by the fact that significant amounts of iso C_(n) alkanes form fromnormal C_(n) alkanes, and normal C_(n) alkanes form from iso C_(n)alkanes initially. The product mixture can contain at least about 2 wt %normal C_(n) alkanes in 1 hr based on the iso C_(n) fraction in thehydrocarbon feed, or at least about 3 wt %, or at least 4 wt %, or atleast about 5 wt %, or at least about 7 wt %, or at least about 10 wt %.The product mixture can contain at least about 5 wt % iso C_(n) alkanesin 1 hr based on the normal C_(n) fraction in the hydrocarbon feed, orat least about 10 wt %, or at least about 15 wt %, or at least about 20wt %.

For normal C₅ isomerization, at least about 10 wt % of iso C₅ formswithin 30 min, or at least about 15 wt %. At least about 15 wt % iso C₅forms within 1 hr, or at least about 20 wt %.

For iso C₅ isomerization, at least about 2 wt % of normal C₅ formswithin 1 hr min, or at least about 3 wt %, or at least about 4 wt %, orat least about 5 wt %.

For normal C₇ isomerization, at least about 5 wt % of iso C₇ formswithin 1 hr, or at least about 10 wt %.

The conversion rate for volume can be calculated as volume rate=(%conversion/time (h))×(mL HC/mL IL), where the mL of IL is determined bytaking the mass of the ionic liquid and carbocation promoter anddividing by the density of the pure ionic liquid. The conversion ratefor volume is at least about 60 in the absence of an added metal salt,or at least about 70, or at least about 80, or at least about 90, or atleast about 100, or at least about 120, or at least about 140, or atleast about 160, or at least about 180, or at least about 200, or atleast about 250, or at least about 300, or at least about 350, or atleast about 400, or at least about 450, or at least about 500.

The conversion rate for mass can be calculated as mass rate=(%conversion/time (h))×(g HC/g IL), where the mass of the IL is taken tobe the summed mass of the IL and carbocation promoter. The conversionrate for mass in the absence of a metal salt is at least about 20, or atleast about 30, or at least about 40, or at least about 50, or at leastabout 60, or at least about 70, or at least about 80, or at least about90, or at least about 100, or at least about 110, or at least about 120,or at least about 130, or at least about 140, or at least about 150, orat least about 175, or at least about 200, or at least about 220 or atleast about 230, or at least about 240, or at least about 250, or atleast about 250.

The present invention provides a method of disproportionating ahydrocarbon feed using less ionic liquid, which is expensive, andobtaining better results at a faster rate. It also provides a method ofisomerizing a hydrocarbon feed using less ionic liquid, and obtainingbetter results at a faster rate.

The hydrocarbon feed can be straight chain paraffins, branched chainparaffins, cycloparaffins, naphthenes, or combinations thereof. Thehydrocarbon feed may contain a single C_(n) alkane, such as pentane, ormixtures of two or more alkanes, such as pentane and hexane, or pentane,hexane, and heptane.

In some embodiments, the hydrocarbon feed can be a mixture of 2, 3, 4,5, or 6 or more consecutive carbon numbers. Typically, there will beone, two, or three carbon numbers that form most of the feed. Forexample, there could be greater than about 50% of one carbon number, orgreater than about 60%, or greater than about 70%, or greater than about80%. In some embodiments, two or three carbon numbers (or more) couldform greater than about 50% of the feed, or greater than about 60%, orgreater than about 70%, or greater than about 80%.

In some embodiments, the C_(n) alkane can be substantially pure C_(n)alkane e.g., greater than about 90% of a C_(n) alkane, such as pentane,or greater than about 95%, or greater than about 97%, or greater thanabout 98%, or greater than about 99%.

In some embodiments, the C_(n) alkane can be substantially pure normalC_(n) alkane or substantially pure iso C_(n) alkane, e.g., greater thanabout 90% of a specific normal or iso C_(n) alkane, such as normalpentane, or greater than about 95%, or greater than about 97%, orgreater than about 98%, or greater than about 99%.

In other embodiments, mixtures of normal C_(n) alkane and iso C_(n)alkane (both a single C_(n) alkane, such as pentane, and two or moreC_(n) alkanes, such as pentane and hexane) are used. The ratio of normalC_(n) alkane to iso C_(n) alkane is typically in the range of about90:10 to about 10:90, or about 80:20 to about 20:80, or about 70:30 toabout 30:70, or about 60:40 to about 40:60, or about 50:50.

As discussed above, the disproportionation reaction of a C_(n) alkaneproduces C_(n−) and C_(n+) alkanes. For example, the disproportionationof C₅ produces C⁴⁻ and C₆₊ alkanes. The presence of the C_(n+) fractiondistinguishes the disproportionation reaction (FIG. 1) fromisomerization reactions which produce isomers of the C_(n) startingmaterial (FIG. 2), or isomerization and cracking which produces isomersof the C_(n) starting material and C_(n−) alkanes due to cracking (FIGS.2 and 3).The hydrocarbon feed can be dried to remove water before beingcontacted with the liquid catalyst. The feed can also be treated toremove undesirable reactive compounds such as alkenes, dienes, nitriles,and the like using known treatment processes.

The hydrocarbon feed can be a fluid. The fluid can be a liquid, a vapor,or a mixture of liquid and vapor. When a liquid or liquid-vapor mixtureis used, the method is one of the few liquid-liquid disproportionationmethods available.

The processes can produce mixtures of alkanes having desirable RVP andRON. The RVP and RON values are calculated on the C₅₊ fraction. The RVPwas calculated as the vapor pressure for the system when thevapor:liquid ratio is 4:1 by volume using the Peng Robinson fluidproperties model. The RON was calculated with linear volumetricblending, and the RON values used for this calculation were based on thevalues listed in Phillips 66 Reference Data for Hydrocarbons andPetro-Sulfur Compounds. Bulletin No. 521.

In one embodiment, the product mixture of alkanes has an RVP in therange of about 1 to about 25, or about 8 to about 16, and an RON in arange of about 50 to about 110, or about 60 to about 100. In anotherembodiment, the product mixture of alkanes has a similar RVP and RON.The octane numbers can be increased by isomerization of the linearparaffins to the corresponding branched compounds.

In some embodiments, the RVP of the product mixture is less than the RVPof the hydrocarbon feed. In some embodiments, the RVP is reduced atleast about 5 numbers compared to the hydrocarbon feed, or at leastabout 7 numbers, or at least about 8 numbers. For example, the RVP forpure (i.e., greater than 99%) normal pentane is 15.6, and the RVP forthe product mixture made from substantially pure normal pentane is 13.0to 13.5. The RVP for pure (i.e., greater than 99%) isopentane is 20.4,and the RVP for the product mixture made from substantially pureisopentane is 12.3 to 12.5.

When the mass ratio of branched alkanes to normal alkanes (i/n) producedfrom converted pentane feed is in the range of about 6:1 to about 17:1,the selectivity for isoparaffins is in the range of about 70 to about90%, and when it is in the range of about 7:1 to about 17:1, theselectivity for isoparaffins is in the range of about 80 to about 90%.The high branched to normal ratios for alkanes obtainable with thissystem are notable, especially in comparison to the methods employingdehydrogenation and metathesis catalysts to effect disproportionation.Generally, when these catalysts are employed, the major isomers formedwithin the C_(n−) and C_(n+) systems are normal paraffins. The formationof large amounts of normal paraffins is typically not desired due totheir low octane numbers.

The formula for calculating the i/n ratio of the product for purealkanes is (wt. % iC_(n−)+x wt. % iC_(n)+wt. % iC_(n+))/(wt. % nC_(n−)+ywt. % nC_(n)+wt. % nC_(n+)) with n− greater than or equal to 4, x=1 andy=0 when C_(n)=normal alkane and x=0 and y=1 when C_(n)=isoalkane. Forexample, for C₅, the calculation would be (wt. % iC₄+x wt. % iC₅+wt. %iC₆+wt. % iC₇+wt. % iC₈)/(wt. % nC₄+y wt. % nC₅+wt. % nC₆+wt. % nC₇+wt.% nC₈); where x=1 and y=0 when C_(n)=nC₅ and x=0 and y=1 when C_(n) isiC₅). Although C₉₊ alkanes will be present in small amounts, they shouldnot substantially affect the i/n ratio as reported. In addition, the C³⁻compounds are not included because they don't have normal and isoisomers.

The lower reactivity of normal pentane (nC₅) has made it generallydifficult to for the development of a commercial process using nC₅.However, disproportionation of nC₅ at reasonable rates has beendemonstrated in more than one embodiment of the present invention.

In order for these reactions to proceed, a stable carbocation likelyneeds to be present. Carbocations readily undergo skeletal rearrangementat low temperatures. Even at −90° C. rapid rearrangement is observed fordegenerate 1, 2-methide shifts. Frequently, carbocations are transientintermediates and are short-lived. However, persistent carbocations havebeen observed in superacidic media.

Ionic liquids offer a number of unique features which make themparticularly well suited as reaction mediums for low temperaturedisproportionation and isomerization. These features include: (1)extremely low volatility, resulting in little to no solvent loss, (2)high chemical diversity, allowing for specific properties to be readilyincorporated into the solvent, (3) good thermal stability, (4) readilyrecyclable, (5) wide liquid ranges, and (6) in some cases (e.g.1-ethyl-3-methylimidazolium chloroahunminates), they have been shown tobe superacidic.

In one embodiment, the liquid hydrocarbon feed comprises a C_(n) alkanewhere n=5-200, or n=5-100, or n=5-50, or n=5-25, or n=5-12. A normalC_(n) alkane is converted to a product mixture comprising iso C_(n)hydrocarbons, normal and iso C_(n−) hydrocarbons and normal and isoC_(n+) hydrocarbons, and an iso C_(n) alkane is converted to a productmixture comprising normal C_(n) hydrocarbons, normal and iso C_(n−)hydrocarbons and normal and iso C_(n+) hydrocarbons. A blend of normaland iso C_(n) alkane is converted to a product mixture comprising normaland iso C_(n) hydrocarbons, normal and iso C_(n−) hydrocarbons andnormal and iso C_(n+) hydrocarbons. In some embodiments, the highestconcentration of C_(n+) hydrocarbons is the C_(n+1) hydrocarbon. Forexample, for a feed of n-pentane, the product mixture would beisopentane, C⁴⁻ hydrocarbons and C₆₊ hydrocarbons, and for a feed ofisopentane, the product mixture would be n-pentane, C⁴⁻ hydrocarbons andC₆₊ hydrocarbons, with the highest concentration being C₆ hydrocarbonsfor the C_(n+) fractions. A feed comprising a blend of n-pentane andisopentane would produce a product mixture of n-pentane and isopentane,C⁴⁻ hydrocarbons and C₆₊ hydrocarbons. The process is particularlyuseful for conversion of C₅, C₆, and C₇ alkanes.

The liquid catalyst comprises an ionic liquid and a carbocationpromoter. The ionic liquid is in liquid form: unlike prior artprocesses, it is not supported on an oxide support. In addition, in someembodiments, the ionic liquids employed herein do not contain Brønstedacids, so the acid concentration within these systems is less than priorart processes using ionic liquids which are Brønsted acidic organiccations. The acid concentration is less than about 2.5 M, or less thanabout 2.25 M, or less than about 2.0 M, or less than about 1.75 M, orless than about 1.5 M. In other embodiments, the ionic liquids docontain Brønsted acids.

One or more ionic liquids can be used.

The ionic liquid comprises an organic cation and an anion. Suitableorganic cations include, but are not limited to:

and lactamium based cations, where R¹-R²¹ are independently selectedfrom C₁-C₂₀ hydrocarbons, C₁-C₂₀ hydrocarbon derivatives, halogens, andH. Suitable hydrocarbons and hydrocarbon derivatives include saturatedand unsaturated hydrocarbons, halogen substituted and partiallysubstituted hydrocarbons and mixtures thereof. C₁-C₅ hydrocarbons areparticularly suitable. Lactamium based ionic liquids include, but arenot limited to, those described in U.S. Pat. No. 8,709,236. U.S.application Ser. No. 14/271,308, entitled Synthesis of Lactam BasedIonic Liquids, filed May 6, 2014, and U.S. application Ser. No.14/271,319, entitled Synthesis of N-Derivatized Lactam Based IonicLiquids, filed May 6, 2014, which are incorporated by reference.

The anion can be derived from halides, sulfates, bisulfates, nitrates,sulfonates, fluoroalkanesulfonates, and combinations thereof. The anionis typically derived from metal and nonmetal halides, such as metal andnonmetal chlorides, bromides, iodides, fluorides, or combinationsthereof. Combinations of halides include, but are not limited to,mixtures of two or more metal or nonmetal halides (e.g., AlCl₄ ⁻ and BF₄⁻), and mixtures of two or more halides with a single metal or nonmetal(e.g. AlCl₃Br⁻). In some embodiments, the metal is aluminum, with themole fraction of aluminum ranging from 0<Al<0.25 in the anion. Suitableanions include, but are not limited to, AlCl₄ ⁻, Al₂Cl₇ ⁻,Al₃Cl₁₀ ⁻,AlCl₃Br⁻, Al₂Cl₆Br⁻, Al₃Cl₉Br⁻, AlBr₄ ⁻, Al₂Br₇ ⁻, Al₃Br₁₀ ⁻, GaCl₄ ⁻,Ga₂Cl₇ ⁻, Ga₃Cl₁₀ ⁻, GaCl₃Br⁻, Ga₂Cl₆Br⁻, Ga₃Cl₉Br⁻, CuCl₂ ⁻, Cu₂Cl₃ ⁻,Cu₃Cl₄ ⁻, ZnCl₃ ⁻, FeCl₃ ⁻, FeCl₄ ⁻, Fe₃Cl₇ ⁻, PF₆ ⁻, and BF₄ ⁻.

The ionic liquid is combined with one or more carbocation promoters. Insome embodiments, the carbocation promoter is added to the ionic liquid.In other embodiments, the carbocation promoter is generated in situ.

Suitable carbocation promoters include, but are not limited to,halo-alkanes, mineral acids alone or combined with alkenes, andcombinations thereof. Suitable halo-alkanes include but are not limitedto 2-chloro-2-methylpropane, 2-chloropropane, 2-chlorobutane,2-chloro-2-methylbutane, 2-chloropentane, 1-chlorohexane,3-chloro-3-methylpentane, or combinations thereof. In some embodiments,the carbocation promoters are not cyclic alkanes.

Suitable mineral acids include, but are not limited to, HCl, HBr, H₂SO₄,and HNO₃. Although HF can also be used, it is less desirable due tosafety issues. If the mineral acid is not strong enough to protonate offa hydrogen from a C—H bond, isobutene or another alkene can be addedwith the mineral acid to produce the desired carbocation promoter. Themineral acid can be generated in situ by the addition of a compound thatreacts with the ionic liquid. In situ acid generation can also occur asa result of reaction with water present in the system. The mineral acidmay also be present as an impurity in the ionic liquid.

2-chloropropane, and 2-chlorobutane were used successfully ascarbocation promoters. HCl was generated in situ by the addition ofmethanol to the ionic liquid, resulting in the partial degradation ofthe Al₂Cl₇ ⁻ anion with concomitant formation of HCl. This method wassufficient to catalyze the disproportionation.

The molar ratio of the carbocation promoter to the ionic liquid in theliquid catalyst is typically in the range of about 0:1 to about 3:1, orabout 0.1:1 to about 1:1. This relates to forming the carbocationpromoter from the halo-alkane or mineral acid. This ratio is importantrelative to the specific type of anion. For example, if the anion isAlCl₄ ⁻, a reaction is unlikely to occur or will be poor because thealuminum is fully coordinated. However, if the anion is Al₂Cl₇ ⁻, thereis some aluminum present that can coordinate to the carbocationpromoter's anion, assisting in generating the carbocation from thecarbocation promoter.

The mass or volume ratios of liquid catalyst (ionic liquid andcarbocation promoter) to hydrocarbon feed are less than 1:1. This isdesirable because the ionic liquid is an expensive component in theprocess. In some embodiments, the mass ratio of ionic liquid tohydrocarbon feed is not more than about 0.75:1, or not more than about0.7:1, or not more than about 0.65:1, or not more than about 0.60:1, ornot more than about 0.55:1, or not more than about 0.50:1. In someembodiments, the volume ratio of ionic liquid to hydrocarbon feed is notmore than about 0.8:1, or not more than about 0.7:1, or not more thanabout 0.6:1, or not more than about 0.5:1, or not more than about0.45:1, or not more than about 0.4:1, or not more than about 0.35:1, ornot more than about 0.3:1, or not more than about 0.25:1.

The liquid hydrocarbon feed is contacted with the liquid catalyst attemperatures of in the range of about −20° C. to the decompositiontemperature of the ionic liquid, or about 250° C. or less, or about 200°C. or less, or about 175° C. or less, or about 150° C. or less, or about125° C. or less, or about 100° C. or less, or about 90° C. or less, orabout 80° C. or less, or about 70° C. or less, or about 60° C. or less,or in the range of about 0° C. to about 250° C., or in the range ofabout 0° C. to about 200° C., or about 0° C. to about 175° C., or about0° C. to about 150° C., or about 10° (to about 150° C., or about 25° C.to about 15° C., or about 30° C. to about 150° C., or about 40° C. toabout 150° C., or about 50° C. to about 150° C. or about 55° C. to about150° C.

The pressure in the reaction zone is typically in the range of about 0MPa to about 20.7 MPa, or about 0 MPa to about 8.1 MPa. In someembodiments, the pressure should be sufficient to ensure that thehydrocarbon feed is in a liquid state. Small amounts of vapor may alsobe present, but this should be minimized. In other embodiments, usingpropane and other light paraffins, the temperatures may not allow for aliquid state. In this gas, a gas phase or a supercritical phase can beused. In some embodiments, a supercritical phase can be used.

In some embodiments, the reaction zone operated at temperatures and orpressures greater than or equal to the critical temperature and pressureof the hydrocarbon feed, such as methane, propane, butanes, pentanes,and hexanes.

The reaction typically takes places in the presence of a gas. Suitablegases include, but are not limited to nitrogen, hydrogen, argon, helium,hydrogen chloride and the like.

The residence time in the reaction zone is generally less than about 10hr, or less than 7 hr, or less than 5 hr, or less than 4 hr, or lessthan 3 hr, or less than 2 hr, or less than 1 hr. The reaction time andconversion are based on the time needed to reach equilibrium of theinitial reaction products, such as 2-methylpentane and isobutane fromthe disproportionation of isopentane. The reaction time is a fiction ofthe degree of mixing, the reaction temperature, the concentration of thecarbocation promoter, the molar ratio of the carbocation promoter toionic liquid, and the mass/volume ratio of ionic liquid to hydrocarbonbeing reacted. Generally, increasing any of these conditions willincrease the reaction rate. Under some conditions, greater than 90%conversion is possible.

The % selectivity for the disproportionation reaction is defined as:[(sum of the wt. % C_(n−) and C_(n+) compounds)/(100−wt. % C_(n)feed)]×100. The % selectivity for the disproportionation reaction istypically at least about 40%, or at least about 45%, or at least about50%, or at least about 55%, or at least about 60%, or at least about65%, or at least about 70%/, or at least about 75%, or at least about80%, or at least about 85%, or at least about 90%, or at least about94%.

For blends, the selectivity for the disproportionation reaction would besimilar as above. For example, for a blend consisting of 50% isopentaneand 50% n-pentane, the % selectivity for the disproportionation reactionis defined as: [(sum of the wt. % C₄— and C₆₊ compounds)/(100−wt. %C_(n) feed)]×100, where the C_(n) feed is taken to be the summed wt. %of isopentane and n-pentane. A simple equation similar to this may notbe adequate for more complex blends.

The % selectivity for the isomerization reaction to isoparaffins(S_(iso-isom)) is defined as (z(wt. % isoparaffin C_(n)))/(100−wt. %C_(n) feed)×100, where z=0 when the C_(n) feed is isoparaffin and z=1when the C_(n) feed is n-paraffin. The % selectivity for isoparaffindisproportionation is defined as (wt. % isoparaffins of C_(n−)+wt. %isoparaffins C_(n+))/(100−wt. % C_(n) feed)×100 (S_(iso-disp)). The %selectivity for isoparaffins is defined as (wt. % isoparaffins ofC_(n−)+wt. % isoparaffins C_(n+)+z(wt. % isoparaffin C_(n)))/(100−wt. %C_(n) feed)×100, where z=0 when the C_(n) feed is isoparaffin and z=1when the C_(n) feed is n-paraffin (S_(isoparaffin)); orS_(isoparaffin)=S_(iso-isom)+S_(iso-disp). The selectivity forisoparaffins is typically at least about 40%, or at least about 45%, orat least about 50%, or at least about 55%, or at least about 60%, or atleast about 65%, or at least about 70%, or at least about 75%, or atleast about 80%, or at least about 85%, or at least about 90%.

For blends, the selectivity for isoparaffins would be similar as above.For example, for a blend consisting of 50% isopentane and 50% n-pentane,the % selectivity for the isoparaffins reaction is defined as: [(sum ofthe wt. % iC₄ and iC₆₊ compounds)/(100−wt. % C_(n) feed)]×100, where theC_(n) feed is taken to be the summed wt. % of isopentane and n-pentane.A simple equation similar to this may not be adequate for more complexblends.

The selectivity is highly dependent on the type of feed used. Forexample, for iC₅, the selectivity for the disproportionation reactiontypically can be in the range of about 92-94%. However, the selectivityfor the disproportionation reaction for nC₅ is much lower, e.g. in therange of about 67-76% because a substantial amount of isomerization toisopentane occurs.

Conversion for the disproportionation and isomerization reactions isdefined as 100−wt. % C_(n) feed. The conversion is typically at leastabout 50%, or at least about 55%, or at least about 60%, or at leastabout 65%, or at least about 70%, or at least about 75%, or at leastabout 80%, or at least about 85%, or at least about 90%.

For blends, the conversion would be the same as above. For example, fora blend consisting of 50% isopentane and 50% n-pentane, the % conversionis equal to 100−wt. % C_(n) feed, where the C_(n) feed taken to be thesummed wt. % of isopentane and n-pentane.

For example, with an iC₅ feed, initially the products are primarily theisoparaffins of the C₄ and C₆ compounds along with some nC₅. Because iC₅is more thermodynamically preferred, the amount of nC₅ that forms isrelatively small, and the dominating pathway is disproportionation.Since the kinetic products are isoparaffins, the selectivity forisoparaffins can be similar to disproportionation. However, the mixtureis not completely at equilibrium, so as the product continues to react,some of the initially formed isoparaffin of the disproportionationproducts begin to convert to their corresponding n-paraffins. As thisoccurs, the selectivity for isoparaffins decreases, but the selectivityfor disproportionation does not.

With a feed of nC₅, the initial products are again primarily theisoparaffins of the C₄ and C₆ compounds and iC₅. Because nC₅ isthermodynamically disfavored the amount of iC₅ that forms issubstantially greater relative to the formation of nC5 from the iC5feed. In this case, significant amounts of nC₅ are converted to iC₅.Since the initial products are isoparaffins, the selectivity forisoparaffins remains high. However, since a significant portion of nC₅is converted to iC₅, the selectivity for disproportionation is less thanit was when iC₅ is used. As the reaction progresses, iC₅ and nC₅continue to disproportionate and the selectivity for disproportionationincreases during the reaction. Conversely, the selectivity forisoparaffins decreases as the mixture equilibrates because the initiallyformed isoparaffin disproportionation products convert to their normalisomers.

At higher temperatures, the relative concentration of normal paraffinsincreases, which ultimately results in decreased selectivities forisoparaffins relative to lower temperatures.

Although the reaction will proceed simply by contacting the hydrocarbonfeed and the liquid catalyst, the reaction rate is generally too slow tobe commercially viable. The reaction rate can be substantially increasedby increasing the stirring speed of the reaction. This indicates thatunder some conditions the rate of reaction is mass transfer limited andis not reflective of the true elementary steps of the reaction. Inaddition to simply stirring the reaction mixture, a baffle can beincluded in the reactor to aid in obtaining good mixing. The bafflehelps to prevent a vortex from forming in the reactor. The formation ofa vortex would reduce the amount of mixing even in the presence ofstirring.

One embodiment of the process 100 is a continuous-flow reactor as shownin FIG. 5. Feed 105, including the liquid hydrocarbon and carbocationpromoter (if present), passes over a drying bed 110 and is continuouslyintroduced to the reactor 115 while simultaneously withdrawing product120. The liquid catalyst (or ionic liquid alone) 112 is introduced tothe reactor 115. The carbocation promoter can be added with thehydrocarbon feed, or with the ionic liquid, or both. The reactordesirably includes a stirrer 160 to mix the hydrocarbon feed 105 and theliquid catalyst. The gaseous products 150 can be separated in thereactor 115. The effluent 120 is sent to a settler 125, where theheavier ionic liquid phase separates as a bottom layer 130. The usedionic liquid stream 165 can be recycled to the reactor 115 and/or theregenerator 135. The upper hydrocarbon layer phase 140 is removed fromthe settler 125, yielding the liquid product 145. The liquid product 145can be separated into two or more product streams (not shown), ifdesired. The gaseous products 170 are separated in settler 125. Thesegaseous products 170 can be combined with gaseous products 150 whichcould then be used as feed in alkylation units (not shown). The usedionic liquid 165 can be regenerated in regenerator 135 to removedeactivated liquid catalyst so it can be reused. Fresh ionic liquid 155can be added to the regenerated ionic liquid stream 175 as needed andsent to the reactor 115. Fresh ionic liquid can also be added to theregenerator 135, as needed.

Another embodiment of the process 100 is a continuous-flow reactor asshown in FIG. 6. A first feed 105, including the first hydrocarbon andcarbocation promoter (if present), passes over a drying bed 110 and iscontinuously introduced to the reactor 115. The second feed 205,including the second hydrocarbon and promoter (if present) passes overdrying bed 210 and is continuously introduced to the reactor 115. Theproduct 120 is simultaneously withdrawn. The liquid catalyst (or ionicliquid alone) 112 is introduced to the reactor 115. The carbocationpromoter can be added with the hydrocarbon feed, or with the ionicliquid, or both. The reactor desirably includes a stirrer 160 to mix thehydrocarbon feeds 105, 205 and the liquid catalyst. The gaseous products150 can be separated in the reactor 115. The effluent 120 is sent to asettler 125, where the heavier ionic liquid phase separates as a bottomlayer 130. The used ionic liquid stream 165 can be recycled to thereactor 115 and/or the regenerator 135. The upper hydrocarbon layerphase 140 is removed from the settler 125, yielding the liquid product145. The liquid product 145 can be separated into two or more productstreams (not shown), if desired. The gaseous products 170 are separatedin settler 125. These gaseous products 170 can be combined with gaseousproducts 150 which could then be used as feed in alkylation units (notshown). The used ionic liquid 165 can be regenerated in regenerator 135to remove deactivated liquid catalyst so it can be reused. Fresh ionicliquid 155 can be added to the regenerated ionic liquid stream 175 asneeded and sent to the reactor 115. Fresh ionic liquid 155 can also beadded to the regenerator 135, as needed.

The ionic liquid can be regenerated in a variety of ways. The ionicliquid containing the conjunct polymer could be contacted with areducing metal (e.g., Al), an inert hydrocarbon (e.g., hexane), andhydrogen and heated to about 100° C. The conjunct polymer will betransferred to the hydrocarbon phase, allowing for the conjunct polymerto be removed from the ionic liquid phase. See e.g., U.S. Pat. No.7,651,970: U.S. Pat. No. 7,825,055; U.S. Pat. No. 7,956,002; U.S. Pat.No. 7,732,363, each of which is incorporated herein by reference.Another method involves contacting the ionic liquid containing theconjunct polymer with a reducing metal (e.g., Al) in the presence of aninert hydrocarbon (e.g. hexane) and heating to about 100° C. Theconjunct polymer will be transferred to the hydrocarbon phase, allowingfor the conjunct polymer to be removed from the ionic liquid phase. Seee.g., U.S. Pat. No. 7,674,739 B2; which is incorporated herein byreference. Still another method of regenerating the ionic liquidinvolves contacting the ionic liquid containing the conjunct polymerwith a reducing metal (e.g., Al), HCl, and an inert hydrocarbon (e.g.hexane), and heating to about 100° C. The conjunct polymer will betransferred to the hydrocarbon phase, allowing for the conjunct polymerto be removed from the IL phase. See e.g., U.S. Pat. No. 7,727,925,which is incorporated herein by reference. The ionic liquid can beregenerated by adding a homogeneous metal hydrogenation catalyst (e.g.,(PPh₃)₃RhCl) to the ionic liquid containing the conjunct polymer and aninert hydrocarbon (e.g. hexane). Hydrogen would be introduced, and theconjunct polymer would be reduced and transferred to the hydrocarbonlayer. See e.g., U.S. Pat. No. 7,678,727, which is incorporated hereinby reference. Another method for regenerating the ionic liquid involvesadding HCl, isobutane, and an inert hydrocarbon to the ionic liquidcontaining the conjunct polymer and heating to about 100° C. Theconjunct polymer would react to form an uncharged complex, which wouldtransfer to the hydrocarbon phase. See e.g., U.S. Pat. No. 7,674,740,which is incorporated herein by reference. The ionic liquid could alsobe regenerated by adding a supported metal hydrogenation catalyst (e.g.Pd/C) to the ionic liquid containing the conjunct polymer and an inerthydrocarbon (e.g. hexane). Hydrogen would be introduced and the conjunctpolymer would be reduced and transferred to the hydrocarbon layer. Seee.g., U.S. Pat. No. 7,691,771, which is incorporated herein byreference. Still another method involves adding a suitable substrate(e.g. pyridine) to the ionic liquid containing the conjunct polymer.After a period of time, an inert hydrocarbon would be added to wash awaythe liberated conjunct polymer. The ionic liquid precursor[butylpyridinium][Cl] would be added to the ionic liquid (e.g.[butylpyridinium][Al₂Cl₇]) containing the conjunct polymer followed byan inert hydrocarbon. After a given time of mixing, the hydrocarbonlayer would be separated, resulting in a regenerated ionic liquid. See,e.g., U.S. Pat. No. 7,737,067, which is incorporated herein byreference. Another method involves adding the ionic liquid containingthe conjunct polymer to a suitable substrate (e.g. pyridine) and anelectrochemical cell containing two aluminum electrodes and an inerthydrocarbon. A voltage would be applied and the current measured todetermine the extent of reduction. After a given time, the inerthydrocarbon would be separated, resulting in a regenerated ionic liquid.See, e.g., U.S. Pat. No. 8,524,623, which is incorporated herein byreference.

The contacting step may be practiced in laboratory scale experimentsthrough full scale commercial operations. The process may be operated inbatch, continuous, or semi-continuous mode. The contacting step can takeplace in various ways, with both concurrent and co-current flowprocesses being suitable.

Disproportionation of nC₅ and iC₅ has also been achieved at temperaturesas low as 45° C. The reaction was faster with iC₅ than with nC₅. Gaschromatograph (GC) analysis revealed that the primary compounds formedwere isoparaffins using the analytical method ASTM UOP690-99; very fewC³⁻ hydrocarbons formed. The products of the reaction for n-C₅ werebroadly divided into the following categories: C³⁻, n-C₄, iC₄, iC₅, C₆paraffins (C₆P) and C₇₊ hydrocarbons. The products of the reaction foriso C₅ were broadly divided into the following categories: C³⁻, n-C₄,iC₄, nC₅, C₆ paraffins (C₆P) and C₇₊ hydrocarbons. The selectivity tothese products was constant over a wide range of isopentane conversions.However, at higher conversions, the selectivity to C₆ paraffinsdecreased, while the selectivity to iC₄ and C₇₊ hydrocarbons increased,which is likely the result of secondary disproportionation-typereactions. An analysis of both the headspace and the liquid phaserevealed that C³⁻ hydrocarbons form in small amounts.

In some places, demand for iC₄ exceeds supply, and disproportionationcould help alleviate this problem.

For iso-pentane conversion, the selectivity to the various products(product selectivity being defined as [wt. % compound/(100−wt. % C_(n)feed)]*100) was nearly constant up to about 52% conversion at 55° C.Higher isopentane conversions resulted in decreased selectivity to C₆paraffins and higher selectivities to iC₄ and C₇₊ hydrocarbons, whichwas likely the result of secondary disproportionation-type reactions.

With iso-pentane conversion, the extent of isomerization to n-pentanewas minimal, but observable, because the reactant was already present inthe more thermodynamically favored state. It was consistently observedthat the selectivity for isomerization of isopentane to n-pentanecentered around 7%, regardless of the % conversion of isopentane.

A significant stir rate dependence on the reaction rate was observed.Under the conditions used, the benefits of increased mixing began totaper off at stir rates greater than 700 rpm, which indicates that muchof the kinetics of the reaction below 700 rpm is mass transfer limited.

The other products that form during the disproportionation reaction ofisopentane were mainly isobutane and C₆₊ isoparaffins. The selectivityto these products was also nearly constant with isopentane conversion.However, at higher conversions, the selectivity to the C₆ paraffinsdecreased, while there was a concomitant increase in selectivity forisobutane and C₇₊ isoparaffins. It is important to note that very littleC³⁻ formed in the reactions at 55° C. as revealed by a headspaceanalysis and by the analytical method ASTM UOP980-07.

Under similar conditions (e.g., volume of ionic liquid, temperature,stir rate, etc.), the rate of nC₅ conversion is dependent on the type ofionic liquid used, as the same reaction proceeds at a much greaterconversion rate in [1-butyl-1-methylpyrrolidinium][Al₂C₇] than in[tributyl(hexyl)phosphonium][Al₂Cl₆Br] ([(^(n)Bu)₃P(Hex)][Al₂Cl₆Br]).Despite the increase in reactivity, the selectivities for the productswere similar to what was observed with the ionic liquid[(^(n)Bu)₃P(Hex)][Al₂Cl₆Br].

Isomerization and disproportionation of n-hexane has been found to occurat temperatures as low as 45° C. in several different ionic liquids(e.g. [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br],[1-butyl-1-methylpyrrolidinium][Al₂Cl₇].[1-butyl-3-methylimidazolium][Al₂Cl₇] andtrihexyl(tetradecyl)phosphonium heptachloroaluminate([(n-Hex)₃P(tetradecyl)][Al₂Cl₇])). The promoter used in all of thesereactions, except for [1-butyl-3-methylimidazolium][Al₂Cl₇], was2-chloro-2-methylpropane, which served to generate the active tert-butylcation. Trace amounts of water or HCl present in[1-butyl-3-methylimidazolium][Al₂Cl₇] was sufficient for the catalysisto occur. A wide range of compounds were formed, including naphthenes,n-paraffins, isoparaffins and even some aromatic complexes, but themajor products are paraffins.

Increasing the concentration of 2-chloro-2-methylpropane increased theconversion, and the yield for the higher and lighter molecular weightcomplexes. The major light components formed were identified byheadspace analysis as iC₄, iC₅, 2-methylpentane and unreacted nC₆.However, it did little to change the selectivity for isomerization.Similarly, increasing the reaction time, temperature, and ratio of massof ionic liquid to mass of hydrocarbon feed increased the overallconversion. It is desirable to minimize the amount of ionic liquid useddue to the cost and potential increase in the amount of feed processedper unit ionic liquid.

By the term “about,” we mean within 10% of the value, or within 5%, orwithin 1%.

EXAMPLES Example 1 Experimental Set Up

The set-up included a 300 mL autoclave equipped with a mechanicalstirrer, pressure gauge, thermocouple, dipleg, rupture disc and valvesto introduce the feed and withdraw an aliquot for GC analysis. Therupture disc vented to a knock out pot. The house nitrogen passedthrough a pressure regulator to a high surface sodium column and wasthen split: feeding to the charger for feed introduction or to a linefor various uses (i.e., 2-methyl-2-chloropropane/C₅P introduction). Thedipleg was constructed such that the height positions it in the paraffinlayer. Upon opening the valve, the withdrawn paraffin layer passedthrough a column of silica, to the GC valve and then through a meteringvalve into a waste container. The reaction mixture was analyzed usingthe ASTM UOP690-99 method. The S_(isoparaffin) was calculated by summingthe wt. % contribution of the C4-C8 isoparaffins that are separableusing the ASTM UOP690-99 method, but does not include the contributionsfrom the C9+ fraction. Consequently, these values represent lower limitsfor the selectivity. Similarly, the S_(iso-disp) were determined usingthis analytical method and is also a lower limit. The RVP was calculatedon the C₅₊ fraction as the vapor pressure for the system when thevapor:liquid ratio is 4:1 by volume using the Peng Robinson fluidproperties model. The RON was calculated on the C₅₊ fraction with linearvolumetric blending and the RON values used for this calculation werebased on the values listed in Phillips 66 Reference Data forHydrocarbons and Petro-Sulfur Compounds. Bulletin No. 521.

Example 2 Synthesis of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br]

An oven-dried round bottom flask was charged with [(^(n)Bu)₃P(Hex)][Br].The material was attached to a rotary evaporator and dried under vacuumat 110° C. for at least 14 h. The dried [(^(n)Bu)₃P(Hex)][Br] wasimmediately brought into a nitrogen glovebox and stored there. Asynthesis was achieved by massing 17.589 g (47.88 mmol) of[(^(n)Bu)₃P(Hex)][Br] into an oven-dried flask equipped with a stir barin the nitrogen glovebox. To this was added 12.775 g (95.81 mmol) ofAlCl₃ at ambient temperature. The mixture was stirred and the solidsslowly reacted over the course of one week to produce a homogenouspale-yellow liquid.

Example 3 Synthesis of [1-butyl-1-methylpyrrolidinium][Al₂Cl₇]

An oven-dried round bottom flask was charged with[1-butyl-1-methylpyrrolidinium][C]. The material was attached to arotary evaporator, dried under vacuum at 110° C. for at least 14 h, andthen sealed under vacuum with a connecting adapter. The dried[1-butyl-1-methylpyrrolidinium][Cl] was immediately brought into anitrogen glovebox and stored there. A synthesis was achieved by massing57.14 g (322 mmol) of [1-butyl-1-methylpyrrolidinium][Cl] into anoven-dried flask equipped with a stir bar in the nitrogen glovebox. Tothis was added 83.93 g (629 mmol) of AlCl₃ at ambient temperature andthe mixture stirred. The solids reacted to produce a homogenous liquid.

Example 4 Synthesis of with [1-butyl-3-methylimidazolium][Al₂Cl₇]

An oven-dried round bottom flask was charged with1-butyl-3-methylimidazolium chloride. The material was attached to arotary evaporator, dried under vacuum at 110° C. for at least 14 h andthen sealed under vacuum with a connecting adapter. Afterwards, thedried 1-butyl-3-methylimidazolium chloride was stored in a nitrogenglovebox. A synthesis was achieved by massing 50.04 g (286 mmol) of1-butyl-3-methylimidazolium chloride into an oven-dried flask equippedwith a stir bar in the nitrogen glovebox. To this was added 76.40 g (573mmol) of AlCl₃ at ambient temperature, and the mixture stirred. Thesolids react to produce a homogenous liquid.

Example 5 iC₅—Stir Rate Effect at 350 rpm with[(^(n)Bu)₃P(Hex)][Al₂Cl₆Br]

A 300 mL stainless steel autoclave, stainless steel baffle, and 75 mLstainless steel sample cylinder were dried in a 120° (oven for at least8 h. The dried autoclave and sample cylinder were brought into anitrogen glovebox and allowed to cool to ambient temperature. Theautoclave was charged with 50.39 g of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br], andthe autoclave head was attached. To the sample cylinder, 1.451 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 119 g of iso-pentane from a pressurizedfeed charger without displacing the nitrogen present in the autoclave.The iso-pentane passed over a high surface sodium column to remove anywater before entering the autoclave. Similarly, the nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. The sample cylinder was charged with 18 g ofiso-pentane using the same method described above and attached to theautoclave. The autoclave was heated to 55° C. and the2-chloro-2-methylpropane/iso-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. After complete addition, theinitial pressure in the autoclave was 145 psi (1 MPa), and the autoclavewas then set to stir at 350 rpm. The reaction was monitored periodicallyby GC. In order to analyze the paraffinic layer, the stirring wasstopped, and the product was allowed to settle for 5 minutes. An aliquotwas sampled directly from the autoclave by opening a valve from theautoclave, passing the paraffinic layer through a SiO₂ column, and thenpassing it directly into a GC sample loop. The mass ratio of liquidcatalyst to iso-pentane was 0.38 and the volume ratio was 0.19. The massrate of reaction was 38, and the volume rate was 75 after 1.4 h. Theresults of the run are shown in Tables 1 and 2.

TABLE 1 Disproportionation and Isomerization of iso-Pentane at 55° C.,350 rpm wt. % of reaction mixture t % S. (h) Conv. C3− iC4 nC4 iC5 nC5C6P C7+ i/n Disp. S_(isoparaffin) 1.4 20 0.00 7.20 0.02 80.46 1.31 6.844.13 11.2 93 82 2.7 28 0.01 10.38 0.04 72.48 2.04 9.93 5.09 9.94 92 844.4 36 0.01 13.64 0.07 64.29 2.70 12.75 6.54 9.48 92 85

TABLE 2 Time (h) 1.4 2.7 4.4 NA Wt. % feed C3P 0.00 0.01 0.01 0.00 C4P7.22 10.43 13.71 0.00 C5P 81.77 74.53 66.99 99.86 C6P 6.84 9.94 12.740.00 C7P 1.67 2.47 3.32 0.00 C8P 0.52 0.73 1.00 0.00 C9+ 1.56 1.51 1.800.00 C5N 0.00 0.00 0.00 0.00 C6N 0.00 0.00 0.00 0.00 C7N 0.01 0.00 0.000.00 C8N 0.34 0.34 0.38 0.00 C6A 0.00 0.00 0.00 0.00 C7A 0.00 0.00 0.000.00 C8A 0.05 0.05 0.05 0.00 nC4-nC5 0.00 0.00 0.00 0.14 unknowns mmoles(based on wt. %) C3P 0 0 0 0 C4P 124 179 236 0 C5P 1133 1033 928 1384C6P 79 115 148 0 C7P 17 25 33 0 C8P 5 6 9 0 C9+ 12 12 14 0 C5N 0 0 0 0C6N 0 0 0 0 C7N 0 0 0 0 C8N 3 3 3 0 C6A 0 0 0 0 C7A 0 0 0 0 C8A 0 0 1 0nC4-nC5 0 0 0 2 unknowns Total mmoles 1374 1374 1372 1386

Example 6 iC5—Stir Rate Effect at 700 rpm with[(^(n)Bu)₃P(Hex)][Al₂Cl₆Br]

A 300 mL stainless steel autoclave, stainless steel baffle, and 75 mLstainless steel sample cylinder were dried in a 120° C. oven for atleast 8 h. The dried autoclave and sample cylinder were brought into anitrogen glovebox and allowed to cool to ambient temperature. Theautoclave was charged with 50.352 g of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br], andthe autoclave head was attached. To the sample cylinder, 1.453 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 112 g of iso-pentane from a pressurizedfeed charger without displacing the nitrogen present in the autoclave.The iso-pentane passed over a high surface sodium column to remove anywater before entering the autoclave. Similarly, the nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. The sample cylinder was charged with 15 g ofiso-pentane using the same method described above and attached to theautoclave. The autoclave was heated to 55° C., and the2-chloro-2-methylpropane/iso-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. After complete addition, theinitial pressure in the autoclave was 115 psi (0.793 MPa), and theautoclave was then set to stir at 700 rpm. The reaction was monitoredperiodically by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The massratio of liquid catalyst to iso-pentane was 0.40 and the volume ratiowas 0.20. The mass rate of reaction was 47, and the volume rate was 93after 1.5 h. The results of the run are shown in Tables 3 and 4.

TABLE 3 Disproportionation and Isomerization of iso-Pentane at 55° C.,700 rpm, wt. % of reaction mixture % S. t (h) Conv. C3− iC4 nC4 iC5 nC5C6P C7+ i/n Disp. S_(isoparaffin) 1.5 28 0.02 10.35 0.04 72.07 1.94 9.835.74 10.5 93 83 2.7 39 0.02 14.84 0.10 61.22 2.82 13.35 7.65 9.5 93 844.4 52 0.03 20.18 0.18 47.98 3.66 16.71 11.25 9.1 93 84

TABLE 4 Time (h) 1.5 2.7 4.4 NA Wt. % feed C3P 0.02 0.02 0.03 0.00 C4P10.39 14.93 20.35 0.00 C5P 74.02 64.05 51.64 99.86 C6P 9.83 13.34 16.710.00 C7P 2.55 3.79 5.53 0.00 C8P 0.82 1.25 1.99 0.00 C9+ 1.99 2.17 3.130.00 C5N 0.00 0.00 0.00 0.00 C6N 0.00 0.00 0.00 0.00 C7N 0.00 0.01 0.010.00 C8N 0.33 0.37 0.51 0.00 C6A 0.00 0.00 0.00 0.00 C7A 0.00 0.00 0.010.00 C8A 0.06 0.06 0.09 0.00 nC4-nC5 0.00 0.00 0.00 0.14 unknowns mmoles(based on wt. %) C3P 0 0 1 0 C4P 179 257 350 0 C5P 1026 888 716 1384 C6P114 155 194 0 C7P 25 38 55 0 C8P 7 11 17 0 C9+ 16 17 24 0 C5N 0 0 0 0C6N 0 0 0 0 C7N 0 0 0 0 C8N 3 3 5 0 C6A 0 0 0 0 C7A 0 0 0 0 C8A 1 1 1 0nC4-nC5 0 0 0 2 unknowns Total mmoles 1371 1370 1363 1386

Example 7 iC5—Stir Rate Effect at 1700 rpm with[(^(n)Bu)₃P(Hex)][Al₂Cl₆Br]

A 300 mL stainless steel autoclave, stainless steel baffle, and 75 mLstainless steel sample cylinder were dried in a 120° C. oven for atleast 8 h. The dried autoclave and sample cylinder were brought into anitrogen glovebox and allowed to cool to ambient temperature. Theautoclave was charged with 50.398 g of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br], andthe autoclave head was attached. To the sample cylinder 1.453 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 106 g of iso-pentane from a pressurizedfeed charger without displacing the nitrogen present in the autoclave.The iso-pentane passed over a high surface sodium column to remove anywater before entering the autoclave. Similarly, the nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. The sample cylinder was charged with 23 g ofiso-pentane using the same method described above and attached to theautoclave. The autoclave was heated to 55° C., and the2-chloro-2-methylpropane/iso-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. After complete addition, theinitial pressure in the autoclave was 139 psi (0.958 MPa), and theautoclave was set to stir at 1700 rpm. The reaction was monitoredperiodically by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The massratio of liquid catalyst to iso-pentane was 0.40 and the volume ratiowas 0.20. The mass rate of reaction was 41, and the volume rate was 82after 2.5 h. The results of the run are shown in Tables 5 and 6.

TABLE 5 Disproportionation and Isomerization of iso-Pentane at 55° C.,1700 rpm, wt. % of reaction mixture % S. t (h) Conv. C3− iC4 nC4 iC5 nC5C6P C7+ i/n Disp. S_(isoparaffin) 2.5 41 0.01 15.70 0.13 58.64 2.9414.48 8.09 9.6 93 84 3.7 49 0.02 19.55 0.19 50.66 3.51 16.73 9.34 9.3 9385

TABLE 6 Time (h) 2.5 3.7 NA Wt. % feed C3P 0.01 0.02 0.00 C4P 15.8319.74 0.00 C5P 61.58 54.17 99.86 C6P 14.48 16.73 0.00 C7P 4.06 4.97 0.00C8P 1.31 1.59 0.00 C9+ 2.30 2.33 0.00 C5N 0.00 0.00 0.00 C6N 0.00 0.000.00 C7N 0.01 0.00 0.00 C8N 0.36 0.39 0.00 C6A 0.00 0.00 0.00 C7A 0.000.01 0.00 C8A 0.06 0.07 0.00 nC4-nC5 0.00 0.00 0.14 unknowns mmoles(based on wt. %) C3P 0 0 0 C4P 272 340 0 C5P 854 751 1384 C6P 168 194 0C7P 41 50 0 C8P 11 14 0 C9+ 18 18 0 C5N 0 0 0 C6N 0 0 0 C7N 0 0 0 C8N 33 0 C6A 0 0 0 C7A 0 0 0 C8A 1 1 0 nC4-nC5 0 0 2 unknowns Total mmoles1368 1371 1386

Example 8 iC5—Stir Rate at 700 rpm with [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br] inHastelloy C Autoclave at 55° C.

A 300 mL Hastelloy C autoclave. Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 120° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 50.416 g of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br], and the autoclavehead was attached. To the sample cylinder 1.422 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 114 g of iso-pentane from a pressurizedfeed charger without displacing the nitrogen present in the autoclave.The iso-pentane passed over a high surface sodium column to remove anywater before entering the autoclave. Similarly, the nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. The sample cylinder was charged with 16 g ofiso-pentane using the same method described above and attached to theautoclave. The autoclave was heated to 55° C., and the2-chloro-2-methylpropane/iso-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. After complete addition, theinitial pressure in the autoclave was 140 psi (0.965 MPa), and theautoclave was set to stir at 700 rpm. The reaction was monitoredperiodically by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The massratio of liquid catalyst to iso-pentane was 0.40 and the volume ratiowas 0.20. The mass rate of reaction was 70, and the volume rate was 140after 0.5 h. The results of the run are shown in Tables 7 and 8.

TABLE 7 Disproportionation and Isomerization of iso-Pentane at 55° C.,700 rpm, Hastelloy C autoclave, wt. % of reaction mixture % S. t (h)Conv. C3− iC4 nC4 iC5 nC5 C6F C7+ i/n Disp. S_(isoparaffin) 0.5 14 0.005.04 0.01 85.85 0.94 4.98 3.16 11.4 93 82 2.8 38 0.14 14.04 0.11 62.483.13 12.89 7.08 8.1 92 83 4.5 54 0.03 20.70 0.25 46.32 4.41 16.82 11.457.6 92 82

TABLE 8 Time (h) 0.5 2.8 4.5 NA Wt. % feed C3P 0.00 0.14 0.03 0.00 C4P5.05 14.16 20.94 0.00 C5P 86.79 65.61 50.73 99.86 C6P 4.99 12.88 16.830.00 C7P 1.19 3.60 5.73 0.00 C8P 0.38 1.15 2.05 0.00 C9+ 1.30 2.07 3.080.00 C5N 0.00 0.00 0.00 0.00 C6N 0.00 0.00 0.00 0.00 C7N 0.00 0.01 0.010.00 C8N 0.25 0.33 0.50 0.00 C6A 0.00 0.00 0.00 0.00 C7A 0.00 0.00 0.010.00 C8A 0.02 0.03 0.05 0.00 nC4-nC5 0.00 0.00 0.00 0.14 unknowns mmoles(based on wt. %) C3P 0 3 1 0 C4P 87 244 360 0 C5P 1203 909 703 1384 C6P58 150 195 0 C7P 12 36 57 0 C8P 3 10 18 0 C9+ 10 16 24 0 C5N 0 0 0 0 C6N0 0 0 0 C7N 0 0 0 0 C8N 2 3 4 0 C6A 0 0 0 0 C7A 0 0 0 0 C8A 0 0 1 0nC4-nC5 0 0 0 2 unknowns Total mmoles 1375 1371 1364 1386

Example 9 iC5—Stir Rate at 700 rpm with[1-Butyl-1-methylimidazolium][Al₂Cl₇] at 55° C. in a Hastelloy CAutoclave

A 300 mL Hastelloy C autoclave. Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 120° C. oven for at least 8. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 55.310 g of [1-butyl-1-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. To the sample cylinder 2.311 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 111 g of iso-pentane from a pressurizedfeed charger without displacing the nitrogen present in the autoclave.The iso-pentane passed over a high surface sodium column to remove anywater before entering the autoclave. Similarly, the nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. The sample cylinder was charged with 28 g ofiso-pentane using the same method described above and attached to theautoclave. The autoclave was heated to 55° C., and the2-chloro-2-methylpropane/iso-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. After complete addition, theinitial pressure in the autoclave was 150 psi (1.034 MPa), and theautoclave was set to stir at 700 rpm. The reaction was monitoredperiodically by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The massratio of liquid catalyst to iso-pentane was 0.41 and the volume ratiowas 0.20. The mass rate of reaction was 150, and the volume rate was 310after 0.6 h. The results of the run are shown in Tables 9 and 10.

TABLE 9 Disproportionation and Isomerization of iso-Pentane at 55° C.,700 rpm, with [1-butyl-3-methylimidazolium][Al₂Cl₇] in a Hastelloy Cautoclave, wt. % of reaction mixture % S. t (h) Conv. C3− iC4 nC4 iC5nC5 C6P C7+ i/n Disp. S_(isoparaffin) 0.6 37 0.01 13.86 0.08 62.83 3.1111.50 8.59 8.2 92 80 1.7 69 0.04 27.55 0.56 31.04 5.47 18.18 17.15 6.992 80 2.9 75 0.07 31.33 1.10 24.52 5.47 18.13 19.38 6.6 93 79 4.5 760.09 32.31 1.56 23.41 5.34 18.37 18.90 6.4 93 80

TABLE 10 Time (h) 0.6 1.7 2.9 4.5 NA Wt. % feed C3P 0.01 0.04 0.07 0.090.00 C4P 13.95 28.12 32.44 33.88 0.00 C5P 65.94 36.51 29.98 28.75 99.86C6P 11.50 18.17 18.12 18.38 0.00 C7P 3.68 7.80 8.61 8.65 0.00 C8P 1.373.36 4.18 4.25 0.00 C9+ 3.01 5.09 5.43 5.09 0.00 C5N 0.00 0.00 0.00 0.000.00 C6N 0.00 0.00 0.00 0.00 0.00 C7N 0.01 0.01 0.01 0.01 0.00 C8N 0.450.84 0.93 0.86 0.00 C6A 0.00 0.00 0.00 0.00 0.00 C7A 0.00 0.03 0.04 0.040.00 C8A 0.08 0.06 0.23 0.06 0.00 nC4-nC5 0.00 0.00 0.00 0.00 0.14unknowns mmoles (based on wt. %) C3P 0 1 2 2 0 C4P 240 484 558 583 0 C5P914 506 416 398 1384 C6P 133 211 210 213 0 C7P 37 78 86 86 0 C8P 12 2937 37 0 C9+ 23 40 42 40 0 C5N 0 0 0 0 0 C6N 0 0 0 0 0 C7N 0 0 0 0 0 C8N4 7 8 8 0 C6A 0 0 0 0 0 C7A 0 0 0 0 0 C8A 1 1 2 1 0 nC4-nC5 0 0 0 0 2unknowns Total mmoles 1365 1357 1361 1368 1386

Example 10 iC5 [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br] in Hastelloy C Autoclave at95° C.

A 300 mL Hastelloy C autoclave. Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 120° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 50.419 g of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br], and the autoclavehead was attached. To the sample cylinder 3.680 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 102 g of iso-pentane from a pressurizedfeed charger without displacing the nitrogen present in the autoclave.The iso-pentane passed over a high surface sodium column to remove anywater before entering the autoclave. Similarly, the nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. The sample cylinder was charged with 15 g ofiso-pentane using the same method described above and then attached tothe autoclave. The autoclave was heated to 95° C., and the2-chloro-2-methylpropane/iso-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. After complete addition, theinitial pressure in the autoclave was 165 psi (1.138 MPa), and theautoclave was set to stir at 1700 μm. The reaction was monitoredperiodically by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The massratio of liquid catalyst to iso-pentane was 0.46 and the volume ratiowas 0.23. The mass rate of reaction was 260, and the volume rate was 520after 0.6 h. The results of the run are shown in Tables 11 and 12.

TABLE 11 Disproportionation and Isomerization of iso-Pentane at 95° C.,wt. % of reaction mixture % S. RVP t (h) Conv. C3− iC4 nC4 iC5 nC5 C6PC7+ i/n Disp. S_(isoparaffin) RON (psi) 0.6 72 0.37 27.78 1.72 28.32 4.216.21 21.36 6.3 94 73 80.0 12.5 1.8 76 0.82 31.73 3.91 23.66 5.4 17.1517.29 4.6 93 76 77.6 12.3 3.1 77 1.05 31.50 5.12 23.14 5.71 17.1 16.384.0 92 74 ND ND 4.6 77 1.21 31.56 6.14 22.79 5.90 16.91 15.42 3.7 92 73ND ND

TABLE 12 Time (h) 0.6 1.8 3.1 4.6 NA Wt. % feed C3P 0.37 0.82 1.05 1.210.00 C4P 29.50 35.64 36.62 37.70 0.00 C5P 32.51 29.06 28.85 28.69 99.86C6P 16.22 17.16 17.10 16.91 0.00 C7P 7.66 8.19 7.96 7.56 0.00 C8P 3.423.88 3.79 3.57 0.00 C9+ 9.74 4.63 4.04 3.81 0.00 C5N 0.00 0.00 0.00 0.000.00 C6N 0.00 0.00 0.00 0.00 0.00 C7N 0.01 0.02 0.02 0.02 0.00 C8N 0.510.56 0.53 0.48 0.00 C6A 0.00 0.00 0.00 0.00 0.00 C7A 0.04 0.04 0.04 0.030.00 C8A 0.01 0.02 0.02 0.02 0.00 nC4-nC5 0.00 0.00 0.00 0.00 0.14unknowns mmoles (based on wt. %) C3P 8 19 24 27 0 C4P 508 613 630 649 0C5P 451 403 400 398 1384 C6P 188 199 198 196 0 C7P 76 82 79 75 0 C8P 3034 33 31 0 C9+ 76 36 31 30 0 C5N 0 0 0 0 0 C6N 0 0 0 0 0 C7N 0 0 0 0 0C8N 5 5 5 4 0 C6A 0 0 0 0 0 C7A 0 0 0 0 0 C8A 0 0 0 0 0 nC4-nC5 0 0 0 02 unknowns Total mmoles 1343 1391 1402 1411 1386

Example 11 nC5 with [(^(n)Bu)₃P(Hex)][AlCl₆Br] at 95° C. in a HastelloyC Autoclave

A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 120° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 50.409 g of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br], and the autoclavehead was attached. To the sample cylinder 3.679 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 102 g of n-pentane from a pressurizedfeed charger without displacing the nitrogen present in the autoclave.The n-pentane passed over a high surface sodium column to remove anywater before entering the autoclave. Similarly, the nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. The sample cylinder was charged with 15 g ofn-pentane using the same method described above and then attached to theautoclave. The autoclave was heated to 95° C., and the2-chloro-2-methylpropane/n-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. After complete addition, theinitial pressure in the autoclave was 160 psi (1.103 MPa), and theautoclave was then set to stir at 1700 rpm. The reaction was monitoredperiodically by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The massratio of liquid catalyst to n-pentane was 0.46 and the volume ratio was0.24. The mass rate of reaction was 130, and the volume rate was 240after 1 h. The results of the nm are shown in Tables 13 and 14.

TABLE 13 Disproportionation and Isomerization of n-Pentane at 95° C.,wt. % of reaction mixture S. t (h) % Conv. C3− iC4 nC4 iC5 nC5 C6P C7+i/n Disp. S_(isoparaffin) S_(iso-isom) 1.0 59 0.42 18.63 1.71 19.4641.34 10.27 8.14 16.9 67 90 33 2.2 70 0.94 22.7 3.08 20.83 29.43 12.5410.30 12.1 70 87 30 3.5 76 0.91 25.1 4.06 21.56 23.72 13.57 11.03 10.472 86 28 4.8 80 1.05 26.39 4.78 21.83 20.06 14.26 11.63 9.4 73 86 27 8.085 1.35 27.64 6.10 21.68 14.82 14.78 12.84 8.0 74 83 25

TABLE 14 Time (h) 1.0 2.2 3.5 4.8 8.0 NA Wt. % feed C3P 0.42 0.94 0.911.05 1.35 0.00 C4P 20.35 25.78 29.16 31.17 33.74 0.00 C5P 60.81 50.2645.28 41.90 36.50 99.60 C6P 10.27 12.55 13.59 14.25 14.78 0.00 C7P 4.175.17 5.67 5.96 6.24 0.00 C8P 1.63 2.11 2.40 2.57 2.82 0.00 C9+ 2.02 2.712.58 2.67 4.10 0.00 C5N 0.00 0.00 0.00 0.00 0.00 0.00 C6N 0.00 0.00 0.000.00 0.00 0.00 C7N 0.01 0.02 0.02 0.02 0.02 0.00 C8N 0.26 0.32 0.36 0.380.41 0.00 C6A 0.00 0.00 0.00 0.00 0.00 0.00 C7A 0.01 0.02 0.02 0.02 0.020.00 C8A 0.06 0.13 0.03 0.03 0.04 0.00 nC4-nC5 0.00 0.00 0.00 0.00 0.000.34 unknowns nC5-nC6 0.00 0.00 0.00 0.00 0.00 0.05 unknowns mmoles(based on wt. %) C3P 10 21 21 24 31 0 C4P 350 444 502 536 580 0 C5P 843697 628 581 506 1380 C6P 119 146 158 165 172 0 C7P 42 52 57 59 62 0 C8P14 18 21 23 25 0 C9+ 16 21 20 21 32 0 C5N 0 0 0 0 0 0 C6N 0 0 0 0 0 0C7N 0 0 0 0 0 0 C8N 2 3 3 3 4 0 C6A 0 0 0 0 0 0 C7A 0 0 0 0 0 0 C8A 1 10 0 0 0 nC4-nC5 0 0 0 0 0 5 unknowns nC5-nC6 0 0 0 0 0 1 unknowns Total1396 1403 1409 1413 1412 1386 mmoles

Example 12 nC5 with [1-butyl-1-methylpyrrolidinium][Al₂Cl₇] at 95° C.

A 300 mL Hastelloy C autoclave. Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 120° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 52.795 g of [1-butyl-1-methylpyrrolidinium][Al₂Cl₇] and theautoclave head was attached. To the sample cylinder 5.24 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 98 g of n-pentane from a pressurized feedcharger without displacing the nitrogen present in the autoclave. Then-pentane passed over a high surface sodium column to remove any waterbefore entering the autoclave. Similarly, the nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. The sample cylinder was charged with 33 g ofn-pentane using the same method described above and attached to theautoclave. The autoclave was heated to 95° C., and the2-chloro-2-methylpropane/n-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. After complete addition, theinitial pressure in the autoclave was 260 psi (1.793 MPa), and theautoclave was set to stir at 1700 rpm. The reaction was monitoredperiodically by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The massratio of liquid catalyst to n-pentane was 0.44 and the volume ratio was0.21. The mass rate of reaction was 220, and the volume rate was 450after 0.6 h. The results of the run are shown in Tables 15 and 16.

TABLE 15 Disproportionation and Isomerization of n-Pentane at 95° C.with [1-butyl-1-methylpyrrolidinium][Al₂Cl₇], wt. % of reaction mixture% S. RVP t (h) Conv. C3− iC4 nC4 iC5 nC5 C6P C7+ i/n Disp.S_(isoparaffin) S_(iso-isom) RON (psi) 0.6 57 0.49 18.16 2.44 18.5542.87 10.02 7.48 13.0 68 89 32 ND ND 1.9 84 1.22 28.59 5.73 22.01 15.6014.75 12.00 8.7 74 85 26 76.1 13.5 3.2 89 1.70 30.42 7.70 21.66 10.5715.38 12.54 7.1 76 83 24 77.1 13.2 4.4 91 1.96 30.79 8.72 21.31 9.0615.51 12.65 6.5 76 81 23 77.4 13.0

TABLE 16 Time (h) 0.6 1.9 3.2 4.4 NA Wt. % feed C3P 0.49 1.22 1.70 1.960.00 C4P 20.60 34.32 38.12 39.51 0.00 C5P 61.41 37.61 32.23 30.37 99.60C6P 10.02 14.76 15.39 15.50 0.00 C7P 3.93 6.04 6.24 6.25 0.00 C8P 1.522.64 2.85 2.89 0.00 C9+ 1.71 2.97 3.00 3.05 0.00 C5N 0.00 0.00 0.00 0.000.00 C6N 0.00 0.00 0.00 0.00 0.00 C7N 0.01 0.01 0.02 0.02 0.00 C8N 0.250.39 0.41 0.41 0.00 C6A 0.00 0.00 0.00 0.00 0.00 C7A 0.01 0.02 0.02 0.020.00 C8A 0.04 0.01 0.02 0.02 0.00 nC4-nC5 0.00 0.00 0.00 0.00 0.34unknowns nC5-nC6 0.00 0.00 0.00 0.00 0.05 unknowns mmoles (based on wt.%) C3P 11 28 39 44 0 C4P 354 591 656 680 0 C5P 851 521 447 421 1380 C6P116 171 179 180 0 C7P 39 60 62 62 0 C8P 13 23 25 25 0 C9+ 13 23 23 24 0C5N 0 0 0 0 0 C6N 0 0 0 0 0 C7N 0 0 0 0 0 C8N 2 4 4 4 0 C6A 0 0 0 0 0C7A 0 0 0 0 0 C8A 0 0 0 0 0 nC4-nC5 0 0 0 0 5 unknowns nC5-nC6 0 0 0 0 1unknowns Total mmoles 1402 1421 1435 1441 1386

Example 13 nC7—Stir Rate at 1700 rpm with [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br] at55° C.-80° C. in a Hastelloy C Autoclave

A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 50.425 g of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br], 201 mL ofn-heptane (pre-dried by storing over activated 3A MS for several days)and then the autoclave head was attached. The sample cylinder wascharged with 8.833 g of a 82.29 wt. % n-heptane and 17.71 wt. %2-chloro-2-methylpropane mixture, both of which had previously beendried over activated sieves. The sample cylinder was closed undernitrogen, and both the autoclave and sample cylinder were removed fromthe glovebox. The autoclave was heated to 55° C. and then the2-chloro-2-methylpropane/n-heptane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to providethis overpressure was passed over a high surface sodium column. Aftercomplete addition, the initial pressure in the autoclave was 340 psi(2.34 MPa), and the autoclave was set to stir at 1700 rpm. The reactionwas monitored by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. After about24 the temperature was increased to 80° C. At the end of the reaction(45 h), an aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and into a sample cylinder. The sample cylinder was then chargedto about 300 psi using nitrogen prior to offline analysis. The massratio of liquid catalyst to n-heptane was 0.36 and the volume ratio was0.20. The mass rate of reaction was 2, and the volume rate was 3 after45 h. The results of the run are shown in Table 17 and were determinedusing the UOP980 method offline.

TABLE 17 Disproportionation and Isomerization of n-heptane at 55-80° C.,1700 rpm, with [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br] in a Hastelloy C autoclave,wt. % of reaction mixture % S. S. Isom. t (h) Conv. C3− iC4 nC4 iC5 nC5C6P nC7 C7P C8P Heavies i/n Disp. C7P 0.0 (feed) NA 0.00 0.00 0.00 0.040.00 0.00 99.25 99.55 0.00 NA NA NA 45 26 0.07 3.90 0.14 3.31 0.16 2.8973.44 15.14

Example 14 nC7—Stir Rate at 1700 rpm with[1-Butyl-1-methylimidazolium][Al₂Cl₇] at 95° C. in a Hastelloy CAutoclave

A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 50 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 5 h andthen placed in a glovebox antechamber and evacuated over night. Theautoclave and sample cylinder were then brought into a nitrogenglovebox. The autoclave was charged with 55.335 g of[1-butyl-1-methylimidazolium][Al₂Cl₇], 211 mL of n-heptane (pre-dried bystoring over activated 3A MS for at least 1 week) and then the autoclavehead was attached. The sample cylinder was charged with 15.358 g of a62.30 wt. % n-heptane and 37.70 wt. % 2-chloro-2-methylpropane mixture,both of which had previously been dried over activated sieves. Thesample cylinder was closed under nitrogen, and both the autoclave andsample cylinder were removed from the glovebox. The autoclave was heatedto 95° C., and then the 2-chloro-2-methylpropane/n-heptane solution inthe sample cylinder was added with an over-pressure of nitrogen. Thenitrogen used to provide this overpressure was passed over a highsurface sodium column. After complete addition, the initial pressure inthe autoclave was 280 psi (1.93 MPa), and the autoclave was set to stirat 1700 rpm. The reaction was monitored by GC. In order to analyze theparaffinic layer, the stirring was stopped, and the product was allowedto settle for 5 minutes. An aliquot was sampled directly from theautoclave by opening a valve from the autoclave, passing the paraffiniclayer through a SiO₂ column, and then passing it directly into a GCsample loop. The mass ratio of liquid catalyst to n-heptane was 0.40 andthe volume ratio was 0.21. The mass rate of reaction was 110, and thevolume rate was 210 after 1 h. The results of the run are shown inTables 18 and 19 and were determined using the UOP690 method.Alternatively, the aliquot could be introduced to a sample cylinder,after passing through the SiO₂ column, and analyzed offline. If thismethod was used, after introduction of the sample to the samplecylinder, the cylinder would then be charged to about 300 psi usingnitrogen prior to offline analysis and analyzed using the UOP980 method.

TABLE 18 Disproportionation and Isomerization of n-heptane at 95° C.,1700 rpm, with [1-butyl-3-methylimidazolium][Al₂Cl₇] in a Hastelloy Cautoclave, wt. % of reaction mixture % S. t (h) Conv. C3− iC4 nC4 iC5nC5 C6P nC7 C7P C8P nC8-nC10 C10+ i/n Disp. S_(iso-isom) 0.0 NA 0.000.00 0.00 0.04 0.00 0.00 99.25 99.55 0.00 NA NA NA (feed) 1.0 44 0.587.63 0.89 7.58 0.77 7.06 66.21 3.26 3.07 2.43 15 77 22

TABLE 19 Time (h) 1.0 NA Wt. % Feed C3P 0.58 0.00 C4P 8.52 0.00 C5P 8.350.04 C6P 7.06 0.00 C7P 66.21 99.55 C8P 3.26 0.00 C9P 1.62 0.00 C10P 1.400.00 C10+ 2.43 0.00 C5N 0.00 0.00 C6N 0.00 0.01 C7N 0.03 0.40 C8N 0.400.00 C6A 0.00 0.00 C7A 0.06 0.00 C8A 0.04 0.00 nC4-nC5 0.00 nC5-nC6 0.000.00 unknowns mmoles (based on wt. %) C3P 13 0 C4P 147 0 C5P 116 1 C6P82 0 C7P 661 993 C8P 29 0 C9P 13 0 C10P 10 0 C10+ 16 0 C5N 0 0 C6N 0 0C7N 0 4 C8N 4 0 C6A 0 0 C7A 1 0 C8A 0 0 nC4-nC5 0 nC5-nC6 0 0 unknownsTotal mmoles 1090 998

Example 15 nC4—Stir Rate at 1700 rpm with [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br] inHastelloy C Autoclave at 95° C.-105° C.

A 300 mL Hastelloy C autoclave. Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 50.467 g of [(^(n)Bu)P(Hex)][Al₂Cl₆Br], and the autoclavehead was attached. To the sample cylinder 3.692 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, was added. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave was charged with 103.1 g of n-butane from a pressurizedfeed charger without displacing the nitrogen present in the autoclave.The sample cylinder was charged with 10.9 g of n-butane using the samemethod described above and attached to the autoclave. The autoclave washeated to 105° C., and the 2-chloro-2-methylpropane/iso-pentane solutionin the sample cylinder was added with an over-pressure of nitrogen. Thenitrogen used to pressurize the charger and for all other work passedover a separate high surface sodium column. After complete addition, theinitial pressure in the autoclave was 420 psi (2.90 MPa), the autoclavewas set to stir at 1700 rpm and the temperature dropped to 101° C. Thetemperature was difficult to maintain above 100° C., so the reaction wascooled to 95° C. where it was easier to maintain temperature. Thereaction was in the 98-101° C. region for about 1 h before being allowedto cool to 95° C. The reaction was monitored periodically by GC offline.In order to analyze the paraffinic layer, the stirring was stopped, andthe product was allowed to settle for 5 minutes. An aliquot was sampleddirectly from the autoclave by opening a valve from the autoclave,passing the paraffinic layer through a SiO₂ column, and into a samplecylinder. The sample cylinder was then charged to about 300 psi usingnitrogen prior to offline analysis. The mass ratio of ionic liquid ton-butane was 0.48 and the volume ratio of ionic liquid:n-butane was 0.22using the following densities: 1.22 g/mL for the liquid catalyst and0.57 g/mL for n-butane. The mass reaction rate was 5, and the volumereaction rate was 10. The results of the run are shown in Table 20 andwere determined using the UOP980 method.

TABLE 20 Disproportionation and Isomerization of n-butane at 95° C.,1700 rpm, Hastelloy C autoclave, wt. % of reaction mixture % S. S. Isomt (h) Conv. C3− iC4 nC4 iC5 nC5 C6P C7+ i/n Disp iC4 0 (feed) 0 0.010.18 99.09 0.00 0.00 0.00 0.60 NA NA NA 3.5 7 0.07 6.76 91.97 0.71 0.080.16 0.14 72 8 92 27.0 15 0.09 13.67 84.53 0.93 0.15 0.17 0.33 80 7 93

Example 16 iC4 and nC7 Reverse Disproportionation—Stir Rate at 1700 rpmwith [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br] in Hastelloy C Autoclave at 95° C.

A 300 mL Hastelloy C autoclave. Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 50.428 g of [(^(n)Bu)₃P(Hex)][Al₂Cl₆Br], 40.368 g ofn-heptane (pre-dried by storing over activated 3A MS for several days)and the autoclave head was attached. To the sample cylinder 1.501 g of2-chloro-2-methylpropane, which had previously been dried over activatedsieves, and 12.868 g of n-heptane was added. The sample cylinder wasclosed under nitrogen, and both the autoclave and sample cylinder wereremoved from the glovebox. The autoclave was charged with 65 g ofiso-butane from a pressurized feed charger without displacing thenitrogen present in the autoclave. The autoclave was heated to 95° C.,and the 2-chloro-2-methylpropane/n-heptane solution in the samplecylinder was added with an over-pressure of nitrogen. The nitrogen usedto pressurize the charger and for all other work passed over a separatehigh surface sodium column. After complete addition, the initialpressure in the autoclave was 360 psi (2.48 MPa) and the autoclave wasset to stir at 1700 rpm. The reaction was monitored periodically by GC.In order to analyze the paraffinic layer, the stirring was stopped, andthe product was allowed to settle for 5 minutes. An aliquot was sampleddirectly from the autoclave by opening a valve from the autoclave,passing the paraffinic layer through a SiO₂ column, and then passing itdirectly into a GC sample loop. At the end of the reaction, an aliquotwas sampled directly from the autoclave by opening a valve from theautoclave, passing the paraffinic layer through a SiO₂ column, and intoa sample cylinder. The sample cylinder was then charged to about 300 psiusing nitrogen prior to offline analysis. The mass ratio of ionic liquidto hydrocarbon feed was 0.44. The volume ratio of ionic liquid tohydrocarbon feed was 0.22 using the following densities: 1.22 g/mL forthe liquid catalyst, 0.68 g/mL for n-heptane and 0.55 g/mL forisobutane. The mass reaction rate was 2, and the volume reaction ratewas 3 after 28 h. The mass reaction rate was 2 and the volume reactionrate was 3 after 21 h. The results of the run are shown in Table 21 andwere determined using the UOP980 method offline. The feed composition (t(O)) is based on the mass of the added reagents.

TABLE 21 Reverse Disproportionation of n-Heptane and iso-Butane at 95°C., 1700 rpm, Hastelloy C autoclave, wt. % of reaction mixture % S. S.Isom. t (h) Conv. C3− iC4 nC4 iC5 nC5 C6P nC7 Heavies i/n Disp. iC4 0(feed) 0 55 45 NA NA NA 28 19 0.27 56.99 1.38 3.16 0.08 1.70 23.80 11.39

Example 17 nC4/nC5—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 55.387 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. 5.6 g of 2-chloro-2-methylpropane, whichhad previously been dried over activated 3A molecular sieves, was addedto the sample cylinder. The sample cylinder was closed under nitrogen,and both the autoclave and sample cylinder were removed from theglovebox. The autoclave was charged with 103 g of n-butane from apressurized feed charger without displacing the nitrogen present in theautoclave, but was then vented down to 86 g of n-butane. The samplecylinder was charged with 31 g of n-pentane from a pressurized feedcharger without displacing the nitrogen present in the sample cylinder.The autoclave was heated to 103° C. while stirring at 100 rpm. Once thistemperature was reached, stirring was stopped and the2-chloro-2-methylpropane/n-pentane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to pressurizethe charger and for all other work passed over a separate high surfacesodium column. After complete addition, the reaction mixture was stirredat 1700 rpm and the temperature increased to 110° C. The pressure in theautoclave at this point was 600 psi (4.14 MPa). After 0.1 h, duringwhich time the temperature fluctuated from 104-111° C., stirring wasstopped, the reaction mixture was allowed to settle for 5 minutes, andthe paraffinic layer was analyzed by GC. An aliquot was sampled directlyfrom the autoclave by opening a valve from the autoclave, passing theparaffinic layer through a SiO₂ column, and then passing it directlyinto a GC sample loop. The GC method employed was UOP690. Afterwards, aliquid sample was removed by filtering through a SiO₂ column into asample cylinder. The liquid contained within the sample cylinder waspressurized with nitrogen to 300 psi (2.07 MPa) and was then analyzedoffline using an analogous method. During sampling, the reaction cooledto 91° C. Afterwards, the reaction was reheated to 100° C. with stirringat 1700 rpm, which took 0.7 h to achieve, and the pressure at this pointwas 350 psi (2.41 MPa). The reaction was continued for an additional17.6 h at this temperature, and the mixture was then analyzed is asimilar manner. The results of the run are shown in Table 22 and weredetermined using the UOP690 method online. The mass ratio of liquidcatalyst to hydrocarbon feed was 0.52, and the volume ratio was 0.23using the following densities: 1.34 g/mL for the liquid catalyst, 0.626g/mL for n-pentane and 0.57 g/mL for n-butane. The mass reaction ratewas 650, and the volume reaction rate was 1500 after 0.1 h.

TABLE 22 Isomerization and disproportionation of a n-butane/n-pentanefeed at 100° C., 1700 rpm, Hastelloy C autoclave, wt. % of feed andreaction mixture HC C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC4-nC5^(b)nC5-nC6^(b) nC8-nC9^(b) nC9-nC10^(b) nC10+^(b) nC5^(a) 0.00 0.00 0.000.03 99.05 0.00 0.00 0.00 0.88 0.03 0.00 0.00 0.00 nC4^(a) 0.01 0.1799.71 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00 time (h) C3P iC4nC4 iC5 nC5 C6P C7P C8P nC4-nC5^(b) nC5-nC6^(b) nC8-nC9^(b) nC9-nC10^(b)nC10+^(b) 0.1 0.44 15.52 52.06 11.64 13.97 3.87 0.81 0.49 0.64 0.11 0.110.06 0.05 18.4 4.35 42.59 24.64 15.16 4.17 6.80 1.03 0.67 0.19 0.00 0.130.05 0.10 ^(a)Composition of the pure hydrocarbon feed, ^(b)Unknownswithin these ranges

Example 18 nC4/nC5—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave. Hastelloy C baffle, and 500 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 55.404 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. 11.821 g of 2-chloro-2-methylpropane, whichhad previously been dried over activated 3A molecular sieves, was addedto a 500 mL sample cylinder. The sample cylinder was closed undernitrogen, and both the autoclave and sample cylinder were removed fromthe glovebox. The sample cylinder was charged with 61.9 g of n-pentane,which was passed over a high surface sodium column, followed by 200.9 gof n-butane from a pressurized feed charger. The sample cylinder wasthen charged to about 600 psi (4.14 MPa) with nitrogen. A portion of thestock solution was analyzed by GC offline. The autoclave was chargedwith 130.3 g of the n-butane/n-pentane/2-chloro-2-methylpropane stocksolution at room temperature, without displacing the nitrogen present inthe autoclave. The initial temperature and pressure were 26° C. and 340psi (2.34 MPa). The reaction mixture was set to stir at 1700 rpm whilethe autoclave was heated to 100° C.; it took 1.2 h to reach temperature,and the initial pressure was 980 psi (6.76 MPa). After a total of 18.8h, the pressure was 1090 psi (7.52 MPa) within the autoclave. At thistime, the reaction mixture was cooled to 85° C. which took 1.6 h, and itwas then analyzed by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The GCmethod employed was UOP690. Afterwards, a liquid sample was removed byfiltering through a SiO₂ column into a sample cylinder. The liquidcontained within the sample cylinder was pressurized with nitrogen toabout 300 psi (2.07 MPa) and was then analyzed offline using ananalogous method. The results of the run are shown in Table 23 and weredetermined using the UOP690 method. The GC of the feed (0.0 h in Table23) is the wt. % of the components in the 500 mL sample cylinder,without integrating 2-chloro-2-methylpropane. The mass ratio of liquidcatalyst to hydrocarbon feed was 0.49, and the volume ratio was 0.21using the following densities: 1.34 g/mL for the liquid catalyst, 0.626g/mL for n-pentane and 0.57 g/mL for n-butane. The mass reaction ratewas 6, and the volume reaction rate was 14 after 20.4 h.

TABLE 23 Isomerization and disproportionation of a n-butane/n-pentanefeed at 100° C., 1700 rpm, Hastelloy C autoclave, wt. % of feed andreaction mixture time (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC4-nC5^(a)nC5-nC6^(a) nC8-nC9^(a) nC9-nC10^(a) nC10+^(a) 0.0 0.01 0.13 73.81 0.0125.26 0.00 0.00 0.00 0.21 0.01 0.00 0.00 0.06 20.4 1.35 40.64 33.7713.40 3.78 5.30 0.73 0.57 0.08 0.00 0.10 0.04 0.09 ^(a)Unknowns withinthese ranges

Example 19 nC4—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 55.394 g of [1-butyl-3-methylimidazolium][Al₂Cl₇] and theautoclave head was attached. 5.818 g of 2-chloro-2-methylpropane, whichhad previously been dried over activated 3A molecular sieves, was addedto the sample cylinder. The sample cylinder was closed under nitrogen,and both the autoclave and sample cylinder were removed from theglovebox. The autoclave was charged with 120 g of n-butane from apressurized feed charger, which was then vented down to 94 g of n-butanein the autoclave. The sample cylinder was charged with 15 g of n-butanefrom a pressurized feed charger without displacing the nitrogen presentin the sample cylinder. The autoclave was heated to 100° C. whilestirring at 138 rpm. Once the temperature was achieved, stirring wasstopped, and the 2-chloro-2-methylpropane/n-butane solution in thesample cylinder was added with an over-pressure of nitrogen. Thenitrogen used to pressurize the charger and for all other work passedover a separate high surface sodium column. After complete addition,stirring was started again at 1700 rpm: the initial pressure in theautoclave was 540 psi (3.72 MPa), and the temperature was 112° C. After0.2 h, during which time the temperature fluctuated from 98-112° C.stirring was stopped, the reaction mixture was allowed to settle, andthe paraffinic layer was analyzed by GC. In order to analyze theparaffinic layer, the stirring was stopped, and the product was allowedto settle for 5 minutes. An aliquot was sampled directly from theautoclave by opening a valve from the autoclave, passing the paraffiniclayer through a SiO₂ column, and then passing it directly into a GCsample loop. The GC method employed was UOP690. Afterwards, a liquidsample was removed by filtering through a SiO₂ column into a samplecylinder. The liquid contained within the sample cylinder waspressurized with nitrogen to 300 psi (2.07 MPa) and was then analyzedoffline using an analogous method. After GC analysis, the reaction wasstirred at 1700 rpm and the temperature had cooled to 96° C. Reheatingto 100° C. took 0.6 h. The reaction was continued for an additional 21.1h at this temperature. The mixture was then analyzed in a similarmanner. The results of the nm are shown in Table 24 and were determinedusing the UOP690 method online. The mass ratio of liquid catalyst tohydrocarbon feed was 0.56, and the volume ratio was 0.24 using thefollowing densities: 1.34 g/mL for the liquid catalyst and 0.57 g/mL forn-butane. The mass reaction rate was 240, and the volume reaction ratewas 570 after 0.2 h.

TABLE 24 Isomerization and disproportionation of n-butane at 100° C.,1700 rpm, Hastelloy C autoclave, wt. % of feed and reaction mixture time(h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC4-nC5^(a) nC5-nC6^(a) nC8-nC9^(a)nC9-nC10^(a) nC10+^(a) 0.0 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.100.00 0.00 0.00 0.00 0.2 0.37 21.55 72.71 3.04 0.77 0.79 0.19 0.31 0.110.00 0.02 0.00 0.05 21.9 0.85 52.78 38.09 5.06 1.38 0.78 0.07 0.30 0.110.00 0.07 0.05 0.15 ^(a)Unknowns within these ranges

Example 20 nC4—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 90° C.

A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 55.392 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. 5.823 g of 2-chloro-2-methylpropane, whichhad previously been dried over activated 3A molecular sieves, was addedto the sample cylinder. The sample cylinder was closed under nitrogen,and both the autoclave and sample cylinder were removed from theglovebox. The autoclave was charged with 117 g of n-butane from apressurized feed charger, which was then vented down to 101 g ofn-butane in the autoclave. The sample cylinder was charged with 15.7 gof n-butane from a pressurized feed charger without displacing thenitrogen present in the sample cylinder. The autoclave was heated to 90°C. with stirring at 115 rpm. Once the temperature had stabilized,stirring was stopped, and the 2-chloro-2-methylpropane/n-butane solutionin the sample cylinder was added with an over-pressure of nitrogen. Thenitrogen used to pressurize the charger and for all other work passedover a separate high surface sodium column. After complete addition, theinitial pressure in the autoclave was 320 psi (2.21 MPa), and theautoclave was set to stir at 1700 rpm. After 97 h, stirring was stoppedand the reaction mixture was allowed to settle and the paraffinic layerwas analyzed by GC. In order to analyze the paraffinic layer, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The GCmethod employed was UOP690. Afterwards, a liquid sample was removed byfiltering through a SiO₂ column into a sample cylinder. The liquidcontained within the sample cylinder was pressurized with nitrogen to300 psi (2.07 MPa) and was then analyzed offline using an analogousmethod. The results of the run are shown in Table 25 and were determinedusing the UOP690 method online. The mass ratio of liquid catalyst tohydrocarbon feed was 0.52, and the volume ratio was 0.22 using thefollowing densities: 1.34 g/mL for the liquid catalyst and 0.57 g/mL forn-butane. The mass reaction rate was 0.8, and the volume reaction ratewas 2 after 97 h.

TABLE 25 Isomerization and disproportionation of n-butane at 90° C.,1700 rpm, Hastelloy C autoclave, wt. % of feed and reaction mixture time(h) C3P iC4 nC4 iC5 nC5 C6P CV C8P nC4-nC5^(a) nC5-nC6^(a) nC8-nC9^(a)nC9-nC10^(a) nC10+^(a) 0.0 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.100.00 0.00 0.00 0.00 97 0.33 33.74 60.38 3.03 0.77 0.61 0.14 0.45 0.110.00 0.08 0.06 0.10 ^(a)Unknowns within these ranges

Example 21 nC4—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave. Hastelloy C baffle, and 500 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 55.390 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. 8.754 g of 2-chloro-2-methylpropane, whichhad previously been dried over activated 3A molecular sieves, was addedto the 500 mL sample cylinder. The sample cylinder was closed undernitrogen, and both the autoclave and sample cylinder were removed fromthe glovebox. Nitrogen and any other gaseous compounds were removed fromthe autoclave by evacuation using standard Schlenk techniques on aSchlenk line. The sample cylinder was charged with 165 g of n-butane.The autoclave was charged with 113 g of then-butane/2-chloro-2-methylpropane stock solution at room temperature.The initial temperature and pressure were 27° C. and 60 psi (0.41 MPa).The reaction mixture was set to stir at 1700 rpm while the autoclave washeated to 100° C. It took 1 h to reach temperature, and the pressure was320 psi (2.21 MPa). After a total of 19.4 h, the pressure was 360 psi(2.48 MPa) within the autoclave. At this time, the reaction mixture wasanalyzed by GC. In order to analyze the paraffinic layer, the stirringwas stopped, and the product was allowed to settle for 5 minutes. Analiquot was sampled directly from the autoclave by opening a valve fromthe autoclave, passing the paraffinic layer through a SiO₂ column, andthen passing it directly into a GC sample loop. The GC method employedwas UOP690. Afterwards, a liquid sample was removed by filtering througha SiO₂ column into a sample cylinder. The liquid contained within thesample cylinder was pressurized with nitrogen to about 300 psi (2.07MPa) and was then analyzed offline using an analogous method. Theresults of the run are shown in Table 26 and were obtained using theUOP690 method. The mass ratio of liquid catalyst to hydrocarbon feed was0.57, and the volume ratio was 0.24 using the following densities: 1.34g/mL for the liquid catalyst and 0.57 g/mL for n-butane. The massreaction rate was 4, and the volume reaction rate was 9 after 19.4 h.

TABLE 26 Isomerization and disproportionation of n-butane feed at 100°C., 1700 rpm, Hastelloy C autoclave, wt % of feed and reaction mixturetime nC4- nC5- (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC5^(a) nC6^(a)nC8-nC9^(a) nC9-nC10^(a) nC10+^(a) iC4/nC4 0.0 0.01 0.17 99.71 0.00 0.000.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00 19.4 0.34 33.54 58.91 4.101.09 1.04 0.19 0.41 0.08 0.00 0.04 0.03 0.08 0.57 ^(a)Unknowns withinthese ranges

Example 22 nC4—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave equipped with a Hastelloy C dipleg andHastelloy B nut and connector, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 55.391 g of [1-butyl-3-methylimidazolium][Al₂Cl₇] and theautoclave head was attached. 5.894 g of 2-chloro-2-methylpropane, whichhad previously been dried over activated 3A molecular sieves, was addedto the sample cylinder. The sample cylinder was closed under nitrogen,and both the autoclave and sample cylinder were removed from theglovebox. The autoclave was charged with 104 g of n-butane from apressurized feed charger without displacing the nitrogen present in theautoclave. The composition of the n-butane feed is listed in Table 27,entry 1. The sample cylinder was charged with 15.25 g of n-butane from apressurized feed charger without displacing the nitrogen present in thesample cylinder. The autoclave was heated to 100° C. with stirring at100 rpm. Once the temperature was reached, stirring was stopped, and the2-chloro-2-methylpropane/n-butane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to pressurizethe charger and for all other work passed over a separate high surfacesodium column. Once the addition was complete, stirring was set to 1700rpm. Initially, the temperature increased to 102° C., and the pressurewas 740 psi (5.10 MPa) within the autoclave. During the first 0.6 h, thetemperature fluctuated from 98-102° C. After this time, the temperaturestabilized at 100° C. and the initial pressure was 720 psi (4.96 MPa).After an additional 7.2 h, the pressure had increased to 830 psi (5.72MPa), and the reaction mixture was analyzed by GC (entry 2. Table 27).In order to analyze the paraffinic layer, the stirring was stopped, andthe product was allowed to settle for 5 minutes. An aliquot was sampleddirectly from the autoclave by opening a valve from the autoclave,passing the paraffinic layer through a SiO₂ column, and then passing itdirectly into a GC sample loop. The GC method employed was UOP690.Afterwards, a liquid sample was removed by filtering through a SiO₂column into a sample cylinder. The liquid contained within the samplecylinder was pressurized with nitrogen to 300 psi (2.07 MPa) and wasthen analyzed offline using an analogous method. Once the stirring wasrecommenced, the temperature increased to 113° C., and, after 0.6 h, itstabilized at 100° C. with a pressure of 410 psi (2.83 MPa). Thereaction was continued for an additional 14.5 h at this temperature, andthe mixture was analyzed is a similar manner (entry 3. Table 27).Afterwards, the autoclave was cooled to ambient temperature, and aportion of the product was vented off. Fresh n-butane was added to thepartially emptied autoclave. The composition of this new mixture isshown in entry 4. Table 27. The autoclave was then heated back to 100°C. with stirring at 1700 rpm, which took 1 h to achieve, and thepressure was 300 psi (2.07 MPa). After an additional 16.9 h of reaction,the product was analyzed. The results of the nm are shown in Table 27and were determined using the UOP690 method online. The mass ratio ofliquid catalyst to hydrocarbon feed was 0.51 and the volume ratio was0.22 using the following densities: 1.34 g/mL for the liquid catalystand 0.57 g/mL for n-butane. The mass reaction rate was 15, and thevolume reaction rate was 35 after 7.8 h.

TABLE 27 Isomerization and disproportionation of n-butane at 100° C.,1700 rpm, Hastelloy C autoclave, wt. % of feed and reaction mixture En-time nC8- nC9- try (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC4-nC5^(a)nC5-nC6^(a) nC9^(a) nC10^(a) nC10+^(a) iC4/nC4 1 0.0 0.01 0.17 99.710.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00 2 7.8 0.97 52.6939.89 4.18 1.13 0.62 0.07 0.23 0.12 0.00 0.00 0.00 0.05 1.32 3 22.9 1.3857.72 33.11 5.19 1.41 0.70 0.05 0.18 0.12 0.00 0.00 0.00 0.07 1.74 422.9 0.66 31.01 64.14 3.03 0.75 0.35 0.00 0.01 0.00 0.00 0.00 0.00 0.000.48 5 40.8 0.72 50.72 42.75 3.75 1.02 0.48 0.04 0.19 0.12 0.00 0.020.01 0.07 1.19 ^(a)Unknowns within these ranges

Example 23 nC4—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C. Using HCl

A 300 mL Hastelloy C autoclave equipped with a Hastelloy C dipleg andHastelloy B nut and connector, and Hastelloy C baffle were dried in a110° C. oven for at least 8 h. The dried autoclave and sample cylinderwere brought into a nitrogen glovebox and allowed to cool to ambienttemperature. The autoclave was charged with 55.390 g of[1-butyl-3-methylimidazolium][Al₂Cl₇], and the autoclave head wasattached. The autoclave was closed under nitrogen and removed from theglovebox. Nitrogen and any other gaseous compounds were removed from theautoclave by evacuation using standard Schlenk techniques and a Schlenkline. The autoclave was charged with 2.5 g of anhydrous HCl at ambienttemperature. Afterwards, 123 g of n-butane was added to the autoclavefrom a pressurized feed charger. The reaction mixture was set to stir at1700 rpm, and the autoclave was heated to 100° C. with stirring at 1700rpm. It took 1.2 h to reach temperature, and the initial pressure was460 psi (3.17 MPa). After a total of 4.8 h, the pressure was 440 psi(3.03 MPa) within the autoclave, and an aliquot was removed for GCanalysis. In order to analyze the paraffinic layer, the stirring wasstopped, and the product was allowed to settle for 5 minutes. An aliquotwas sampled directly from the autoclave by opening a valve from theautoclave, passing the paraffinic layer through a SiO₂ column, and thenpassing it directly into a GC sample loop. The GC method employed wasUOP690 (entry 2. Table 28). Entry 1 in Table 28 is the composition ofthe butane feed. Afterwards, a liquid sample was removed by filteringthrough a SiO₂ column into a sample cylinder. The liquid containedwithin the sample cylinder was pressurized with nitrogen to 300 psi(2.07 MPa) and was then analyzed offline using an analogous method.Afterwards, stirring was set to 1700 rpm, and the pressure was 320 psi(2.21 MPa). The reaction was continued for an additional 17.0 h thepressure was 320 psi (2.21 MPa) and had not increased. The reactiontemperature was increased to 120° C.; it took 1 h to reach temperature.At this temperature, the pressure within the autoclave was 510 psi (3.52MPa). The reaction was stirred at this temperature for 3.9 h, and thepressure had increased to 530 psi (3.65 MPa). The temperature was thenincreased to 130° C. It took 0.5 h to reach temperature, and thereaction was allowed to continue at that temperature for an additional2.7 h. Afterwards, the temperature was decreased to 100° C.; it took 0.7h to reach temperature. After maintaining the temperature at 100° C. for0.1 h, the pressure within the autoclave was 350 psi (2.41 MPa), and theproduct mixture was analyzed in a similar manner (entry 3, Table 28), asdiscussed above. Afterwards, stirring was set to 1700 rpm, and thereaction mixture heated to 120° C. It took 1.1 h to reach temperature,and the pressure at this temperature was 500 psi (3.45 MPa). Thereaction mixture was allowed to continue to react at this temperaturefor an additional 13.5 h. At this time, the pressure within theautoclave was 510 psi (3.52 MPa). The reaction mixture was then cooledto 24° C. and analyzed by GC (entry 4, Table 28). The results of the runare shown in Table 28 and were determined using the UOP690 methodonline. The mass ratio of liquid catalyst to hydrocarbon feed was 0.47,and the volume ratio was 0.20 using the following densities: 1.34 g/mLfor the liquid catalyst and 0.57 g/mL for n-butane. The mass reactionrate was 3, and the volume reaction rate was 8 after 4.8 h.

TABLE 28 Isomerization and disproportionation of n-butane at 100-130° C.Using HCl, 1700 rpm, Hastelloy C autoclave, wt. % of feed and reactionmixture En- time nC4- nC5- nC8- nC9- iC4/ % C4P try (h) C3P iC4 nC4 iC5nC5 C6P C7P C8P nC5^(a) nC6^(a) nC9^(a) nC10^(a) nC10+^(a) nC4 Conv. 10.0 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.000.00 0 2 4.8 0.01 7.37 92.45 0.00 0.00 0.00 0.00 0.00 0.16 0.00 0.000.00 0.00 0.08 7 3 30.7 0.34 57.95 40.95 0.46 0.13 0.00 0.00 0.02 0.120.00 0.00 0.00 0.00 1.42 59 4 45.3 2.11 59.83 33.93 3.00 0.82 0.13 0.000.00 0.12 0.00 0.00 0.00 0.00 1.76 66 ^(a)Unknowns within these ranges

Example 24 GC Method and Procedure for Offline Analysis

The sample cylinder containing the hydrocarbon product was positioned sothat it was held vertically in a hood or well-vented area and connectedto the GC by means of 1/16″ stainless steel capillary tubing. Thecapillary tubing led to an LPG injection valve with a 0.5 μL sampleloop. The exit of the injection valve used ⅛″ translucent FEP Teflonrated to 500 psig, which was connected to a shutoff valve, which thenled to a vent. The injection valve was put into the fill position, andthe vent shut-off valve was closed. The bottom valve on the samplecylinder was opened, and the vent shut-off valve was partially opened topermit the flow of the hydrocarbon product. Once the entrained bubblesare no longer observed in the translucent tubing, the vent shut-offvalve was closed. The sample was injected immediately by switching theinjection valve to the injection position, and starting the integratorand the column temperature programming sequence. The injection valveremains in the inject position for the duration of the sample run. Thevalve on the sample cylinder was immediately closed, and the ventshut-off valve was opened to vent the sampling system. The GC columnused was a 100 m 0.25 mm ID fused silica capillary column, internallycoated to a film thickness of 0.5 μm with crosslinked dimethylpolysiloxane, Petrocol DH, Supelco. Cat. No. 24160-U. The GC method useda flame ionization detector. The carrier gas was hydrogen and operatedin the constant pressure mode at an equivalent flow at 34° C. of 2.3mL/min. The split flow rate was 200 mL/min, and the injection porttemperature was 215° C. The initial column temperature was 34° C., andit was held for 15 minutes at this temperature. The temperature was thenramped to 75° C. at 8° C./min ramp rate and held at 75° C. for 15minutes. The temperature was then ramped to 250° C. at 20° C./min ramprate and held at 250° C. for 22 minutes. The detector temperature was250° C. with a hydrogen flow rate of 30 mL/min and an air flow rate of400 mL/min. The makeup gas can be either nitrogen or helium and was setat 30 mL/min. There were 76 components identified.

Example 25 Modification of the GC Method Used for Analysis of theReaction with the FT Wax

The GC method used to quantify the products from the reaction with theFT wax was a modification of the UOP690 method used for online analysis.The inlet temperature was increased to 265° C., and the run time andtemperature were increased. At the end of the temperature programemployed in the UOP690 method, instead of ending the run, thetemperature was increased to 315° C. at a ramp rate of 20° C./min andheld at that temperature for 35 minutes.

Example 26 nC4/nC7—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave equipped with a Hastelloy C dipleg andHastelloy B nut and connector, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.339 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with4.024 g of 2-chloro-2-methylpropane, and 12.228 g of n-heptane, bothcompounds having previously been dried over activated 3A molecularsieves. The sample cylinder was closed under nitrogen, and both theautoclave and sample cylinder were removed from the glovebox. Theautoclave was charged with 111 g of n-butane from a pressurized feedcharger without displacing the nitrogen present in the autoclave. Thecomposition of the n-butane feed is listed in Table 29, entry 1. Theautoclave was heated to 100° C. with stirring at 100 rpm. Once thetemperature was reached, stirring was stopped, and the2-chloro-2-methylpropane-heptane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to pressurizethe charger and for all other work passed over a separate high surfacesodium column. Once the addition was complete, stirring was set to 1700rpm. Initially, the temperature increased to 110° C., and the pressurewas 460 psi (3.17 MPa) within the autoclave. After 8 minutes ofstirring, the temperature decreased to 105° C., and the pressure was 360psi (2.48 MPa). After 8 minutes, stirring was stopped and the paraffiniclayer was analyzed by online and offline GC. In order to analyze theparaffinic layer with online GC, the stirring was stopped, and theproduct was allowed to settle for 5 minutes. An aliquot was sampleddirectly from the autoclave by opening a valve from the autoclave,passing the paraffinic layer through a SiO₂ column, and then passing itdirectly into a GC sample loop. The GC method employed was UOP690.Afterwards, a liquid sample was removed by filtering through a SiO₂column into a sample cylinder for offline GC analysis. The liquidcontained within the sample cylinder was pressurized with nitrogen toabout 300 psi (2.07 MPa) and was then analyzed offline using ananalogous method as described above. The reported results are those fromthe offline analysis and are depicted in Table 29. This procedure wasrepeated two more times and the results are reported in Table 29. Afterstirring was recommenced, the temperature stabilized at 100° C. after anadditional 42 minutes of reaction. The mass ratio of liquid catalyst tohydrocarbon feed was 0.34, and the volume ratio was 0.15 using thefollowing densities: 1.34 g/mL for the liquid catalyst, 0.684 g/mL forn-heptane and 0.57 g/mL for n-butane.

TABLE 29 Reverse disproportionation of an n-butane/n-heptane feed at100° C., 1700 rpm, Hastelloy C autoclave, wt. % of feed and reactionmixture time (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P Other^(a) C4P C5PiC4/nC4 iC5/nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.11 99.880.00 0.00 NA 0.0^(b) 0.0 0.0 90.1 0.0 0.0 0.0 9.9 0.0 0.0 90.1 0.0 0.0NA 0.1 0.71 12.67 73.35 4.15 0.67 1.81 5.83 0.38 0.43 86.02 4.82 0.176.19 4.5 2.36 40.53 38.24 10.74 2.83 3.60 0.81 0.49 0.40 78.77 13.571.06 3.80 17.6 5.25 50.62 26.53 10.77 2.77 2.89 0.37 0.23 0.57 77.1513.54 1.91 3.89 ^(a)Other compounds present, ^(b)wt. % composition at t= 0 h is based on mass of added reagents

Example 27 nC4/nC9—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave equipped with a Hastelloy C dipleg andHastelloy B nut and connector, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.34 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with4.02 g of 2-chloro-2-methylpropane and 15.65 g of n-nonane, bothcompounds having previously been dried over activated 3A molecularsieves. The sample cylinder was closed under nitrogen, and both theautoclave and sample cylinder were removed from the glovebox. Theautoclave was charged with 111 g of n-butane from a pressurized feedcharger without displacing the nitrogen present in the autoclave. Thecomposition of the n-butane feed is listed in Table 30, entry 1. Theautoclave was heated to 100° C. with stirring at 100 rpm. Once thetemperature was reached, stirring was stopped, and the2-chloro-2-methylpropane/n-nonane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to pressurizethe charger and for all other work passed over a separate high surfacesodium column. Once the addition was complete, stirring was set to 1700rpm. Initially, the temperature increased to 105° C., and the pressurewas 520 psi (3.58 MPa) within the autoclave. After 9 minutes ofstirring, the temperature decreased to 101° C., and the pressure was 355psi (2.45 MPa). After 9 minutes, stirring was stopped, and theparaffinic layer was analyzed by online and offline GC. In order toanalyze the paraffinic layer with online GC, the stirring was stopped,and the product was allowed to settle for 5 minutes. An aliquot wassampled directly from the autoclave by opening a valve from theautoclave, passing the paraffinic layer through a SiO₂ column, and thenpassing it directly into a GC sample loop. The GC method employed wasUOP690. Afterwards, a liquid sample was removed by filtering through aSiO₂ column into a sample cylinder for offline GC analysis. The liquidcontained within the sample cylinder was pressurized with nitrogen toabout 300 psi (2.07 MPa) and was then analyzed offline using ananalogous method as described above. The reported results are those fromthe offline analysis and are depicted in Table 30. This procedure wasrepeated two more times and the results are reported in Table 30. Afterstirring was recommenced, the temperature stabilized at 100° C. after anadditional 27 minutes of reaction. The mass ratio of liquid catalyst tohydrocarbon feed was 0.33, and the volume ratio was 0.14 using thefollowing densities: 1.34 g/mL for the liquid catalyst, 0.718 g/mL forn-nonane and 0.57 g/mL for n-butane.

TABLE 30 Reverse disproportionation of an n-butane/n-nonane feed at 100°C., 700 rpm, Hastelloy C autoclave, wt. % of feed and reaction mixturetime iC4/ iC5/ (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC9 C9+ Other^(a) C4PC5P nC4 nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.1199.88 0.00 0.00 NA 0.0^(b) 0.0 0.0 87.6 0.0 0.0 0.0 0.0 0.0 12.4 0.000.0 90.1 0.0 0.0 NA 0.2 0.43 13.31 71.62 5.27 0.76 2.04 0.86 0.57 4.140.59 0.41 84.93 6.03 0.18 6.93 4.6 1.68 37.39 39.82 11.60 2.95 4.23 1.040.67 0.04 0.28 0.30 77.21 14.55 0.94 3.93 21.1 3.38 48.92 27.50 11.823.05 3.97 0.59 0.35 0.01 0.19 0.22 76.42 14.87 1.78 3.88 ^(a)Othercompounds present, ^(b)wt. % composition at t = 0 h is based on mass ofadded reagents

Example 28 nC4/nC9—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave equipped with a Hastelloy C dipleg andHastelloy B nut and connector, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.341 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with4.038 g of 2-chloro-2-methylpropane and 43.003 g of n-nonane, bothcompounds having previously been dried over activated 3A molecularsieves. The sample cylinder was closed under nitrogen, and both theautoclave and sample cylinder were removed from the glovebox. Theautoclave was charged with 89 g of n-butane from a pressurized feedcharger without displacing the nitrogen present in the autoclave. Thecomposition of the n-butane feed is listed in Table 31, entry 1. Theautoclave was heated to 100° C. with stirring at 100 rpm. Once thetemperature was reached, stirring was stopped, and the2-chloro-2-methylpropane/n-nonane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to pressurizethe charger and for all other work passed over a separate high surfacesodium column. Once the addition was complete, stirring was set to 1700rpm. Initially, the temperature increased to 114° C., and the pressurewas 505 psi (3.48 MPa) within the autoclave. After 7 minutes ofstirring, the temperature decreased to 106° C., and the pressure was 400psi (2.76 MPa). After 7 minutes, stirring was stopped, and theparaffinic layer was analyzed by online and offline GC. In order toanalyze the paraffinic layer with online GC, the stirring was stopped,and the product was allowed to settle for 5 minutes. An aliquot wassampled directly from the autoclave by opening a valve from theautoclave, passing the paraffinic layer through a SiO₂ column, and thenpassing it directly into a GC sample loop. The GC method employed wasUOP690. Afterwards, a liquid sample was removed by filtering through aSiO₂ column into a sample cylinder for offline GC analysis. The liquidcontained within the sample cylinder was pressurized with nitrogen toabout 300 psi (2.07 MPa) and was then analyzed offline using ananalogous method as described above. The reported results are those fromthe offline analysis and are depicted in Table 31. This procedure wasrepeated two more times and the results are reported in Table 31. Afterstirring was recommenced, the temperature stabilized at 100° C. after anadditional 18 minutes of reaction. The mass ratio of liquid catalyst tohydrocarbon feed was 0.32, and the volume ratio was 0.15 using thefollowing densities: 1.34 g/mL for the liquid catalyst, 0.718 g/mL forn-nonane and 0.57 g/mL for n-butane.

TABLE 31 Reverse disproportionation of an n-butane/n-nonane feed at 100°C., 1700 rpm, Hastelloy C autoclave, wt. % of feed and reaction mixturetime iC4/ iC5/ (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC9 C9+ Other^(a) C4PC5P nC4 nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.1199.88 0.00 0.00 NA 0.0^(b) 0.0 0.0 67.4 0.0 0.0 0.0 0.0 0.0 32.6 0.000.0 67.4 0.0 0.0 NA 0.1 0.54 11.31 59.02 6.45 0.82 3.03 1.35 0.82 14.761.37 0.53 70.33 7.27 0.19 7.87 4.6 1.03 21.34 45.76 12.49 2.16 6.37 2.621.29 4.64 1.59 0.71 67.1 14.65 0.47 5.78 23.4 1.34 27.88 37.76 15.043.35 7.74 2.77 1.24 0.90 1.34 0.64 65.64 18.39 0.74 4.49 ^(a)Othercompounds present, ^(b)wt. % composition at t = 0 h is based on mass ofadded reagents

Example 29 nC4/nC9—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₄Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave equipped with a Hastelloy C dipleg andHastelloy B nut and connector. Hastelloy C baffle, and 150 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.34 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 150 mL sample cylinder was charged with4.02 g of 2-chloro-2-methylpropane and 87.82 g of n-nonane, bothcompounds having previously been dried over activated 3A molecularsieves. The sample cylinder was closed under nitrogen, and both theautoclave and sample cylinder were removed from the glovebox. Theautoclave was charged with 60 g of n-butane from a pressurized feedcharger without displacing the nitrogen present in the autoclave. Thecomposition of the n-butane feed is listed in Table 32, entry 1. Theautoclave was heated to 100° C. with stirring at 100 rpm. Once thetemperature was reached, stirring was stopped, and the2-chloro-2-methylpropane/n-nonane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to pressurizethe charger and for all other work passed over a separate high surfacesodium column. Once the addition was complete, stirring was set to 1700rpm. Initially, the temperature increased to 109° C., and the pressurewas 460 psi (3.17 MPa) within the autoclave. After 7 minutes ofstirring, the temperature decreased to 104° C., and the pressure was 440psi (3.03 MPa). After 7 minutes, stirring was stopped, and theparaffinic layer was analyzed by online and offline GC. In order toanalyze the paraffinic layer with online GC, the stirring was stopped,and the product was allowed to settle for 5 minutes. An aliquot wassampled directly from the autoclave by opening a valve from theautoclave, passing the paraffinic layer through a SiO₂ column, and thenpassing it directly into a GC sample loop. The GC method employed wasUOP690. Afterwards, a liquid sample was removed by filtering through aSiO₂ column into a sample cylinder for offline GC analysis. The liquidcontained within the sample cylinder was pressurized with nitrogen toabout 300 psi (2.07 MPa) and was then analyzed offline using ananalogous method as described above. The reported results are those fromthe offline analysis and are depicted in Table 32. This procedure wasrepeated two more times and the results are reported in Table 32. Afterstirring was recommenced, the temperature stabilized at 100° C. after anadditional 38 minutes of reaction. The mass ratio of liquid catalyst tohydrocarbon feed was 0.29, and the volume ratio was 0.14 using thefollowing densities: 1.34 g/mL for the liquid catalyst, 0.718 g/mL forn-nonane and 0.57 g/mL for n-butane.

TABLE 32 Reverse disproportionation of an n-butane/n-nonane feed at 100°C., 1700 rpm, Hastelloy C autoclave, wt. % of feed and reaction mixturetime (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC9 C9+ Other^(a) C4P C5PiC4/nC4 iC5/nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.00 0.000.11 99.88 0.00 0.00 NA 0.0^(b) 0.0 0.0 40.6 0.0 0.0 0.0 0.0 0.0 59.40.00 0.0 40.6 0.0 0.0 NA 0.1 0.33 7.72 38.45 5.77 0.58 3.08 1.58 0.9538.61 2.16 0.77 46.17 6.35 0.20 9.95 4.7 0.56 12.03 35.91 9.05 1.06 5.042.55 1.44 28.22 3.23 0.91 47.94 10.11 0.34 8.54 22.8 0.60 13.44 35.829.92 1.23 5.62 2.79 1.50 24.69 3.46 0.93 49.26 11.15 0.38 8.07 ^(a)Othercompounds present, ^(b)wt. % composition at t = 0 h is based on mass ofadded reagents

Example 30 nC4/nC16—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave equipped with a Hastelloy C dipleg andHastelloy B nut and connector, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.34 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with3.9 g of 2-chloro-2-methylpropane and 27.1 g of n-hexadecane, bothcompounds having previously been dried over activated 3A molecularsieves. The sample cylinder was closed under nitrogen, and both theautoclave and sample cylinder were removed from the glovebox. Theautoclave was charged with 111 g of n-butane from a pressurized feedcharger without displacing the nitrogen present in the autoclave. Thecomposition of the n-butane feed is listed in Table 33, entry 1. Theautoclave was heated to 100° C. with stirring at 100 rpm. Once thetemperature was reached, stirring was stopped, and the2-chloro-2-methylpropane/n-hexadecane solution in the sample cylinderwas added with an over-pressure of nitrogen. The nitrogen used topressurize the charger and for all other work passed over a separatehigh surface sodium column. Once the addition was complete, stirring wasset to 1700 rpm. Initially, the temperature increased to 105° C., andthe pressure was 650 psi (4.48 MPa) within the autoclave. After 18minutes of stirring, the temperature decreased to 98° C., and thepressure was 490 psi (3.38 MPa). After 18 minutes, stirring was stoppedand the paraffinic layer analyzed by online and offline GC. In order toanalyze the paraffinic layer with online GC, the stirring was stopped,and the product was allowed to settle for 5 minutes. An aliquot wassampled directly from the autoclave by opening a valve from theautoclave, passing the paraffinic layer through a SiO₂ column, and thenpassing it directly into a GC sample loop. The GC method employed wasUOP690. Afterwards, a liquid sample was removed by filtering through aSiO₂ column into a sample cylinder for offline GC analysis. The liquidcontained within the sample cylinder was pressurized with nitrogen toabout 300 psi (2.07 MPa) and was then analyzed offline using ananalogous method as described above. The reported results are those fromthe offline analysis and are depicted in Table 33. This procedure wasrepeated two more times and the results are reported in Table 33. Afterstirring was recommenced, the temperature stabilized at 10° C. after anadditional 40 minutes of reaction. The mass ratio of liquid catalyst tohydrocarbon feed was 0.30, and the volume ratio was 0.14 using thefollowing densities: 1.34 g/mL for the liquid catalyst, 0.773 g/mL forn-hexadecane and 0.57 g/mL for n-butane.

TABLE 33 Reverse disproportionation of an n-butane/n-hexadecane feed at100° C., 1700 rpm, Hastelloy C autoclave, wt. % of feed and reactionmixture time (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC16 C9+ Other^(a) C4PC5P iC4/nC4 iC5/nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.000.00 0.11 99.88 0.00 0.00 NA 0.0^(b) 0.0 0.0 80.4 0.0 0.0 0.0 0.0 0.019.6 0.00 0.0 80.4 0.0 0.0 NA 0.3 0.41 11.40 68.77 5.85 0.78 2.85 1.340.72 6.38 1.06 0.44 80.17 6.63 0.17 7.50 4.8 1.51 26.24 39.95 13.45 2.886.92 2.65 1.24 3.38 1.20 0.58 66.19 16.33 0.66 4.67 23.5 2.36 34.2529.63 16.09 4.11 8.08 2.45 1.11 0.46 0.90 0.56 63.88 20.2 1.16 3.91^(a)Other compounds present, ^(b)wt. % composition at t = 0 h is basedon mass of added reagents

Example 31 nC4/nC7—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy C autoclave equipped with a Hastelloy C dipleg andHastelloy B nut and connector, Hastelloy C baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.342 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with4.020 g of 2-chloro-2-methylpropane and 12.232 g of n-heptane, bothcompounds having previously been dried over activated 3A molecularsieves. The sample cylinder was closed under nitrogen, and both theautoclave and sample cylinder were removed from the glovebox. Theautoclave was charged with 113 g of n-butane from a pressurized feedcharger without displacing the nitrogen present in the autoclave. Thecomposition of the n-butane feed is listed in Table 34, entry 1. Theautoclave was heated to 100° C. with stirring at 100 rpm. Once thetemperature was reached, stirring was stopped, and the2-chloro-2-methylpropane/n-heptane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to pressurizethe charger and for all other work passed over a separate high surfacesodium column. Once the addition was complete, stirring was set to 1700rpm. Initially, the temperature increased to 101° C., and the pressurewas 500 psi (3.45 MPa) within the autoclave. After 9 minutes ofstirring, the temperature decreased to 99° C., and the pressure was 450psi (3.10 MPa). After 9 minutes, stirring was stopped, and theparaffinic layer was analyzed by online and offline GC. In order toanalyze the paraffinic layer with online GC, the stirring was stopped,and the product was allowed to settle for 5 minutes. An aliquot wassampled directly from the autoclave by opening a valve from theautoclave, passing the paraffinic layer through a SiO₂ column, and thenpassing it directly into a GC sample loop. The GC method employed wasUOP690. Afterwards, a liquid sample was removed by filtering through aSiO₂ column into a sample cylinder for offline GC analysis. The liquidcontained within the sample cylinder was pressurized with nitrogen toabout 300 psi (2.07 MPa) and was then analyzed offline using ananalogous method as described above. The reported results are those fromthe offline analysis and are depicted in Table 34. This procedure wasrepeated two more times and the results are reported in Table 34. Afterstirring was recommenced, the temperature stabilized at 100° C. after anadditional 38 minutes of reaction. The mass ratio of liquid catalyst tohydrocarbon feed was 0.34, and the volume ratio was 0.15 using thefollowing densities: 1.34 g/mL for the liquid catalyst, 0.684 g/mL forn-heptane and 0.57 g/mL for n-butane.

TABLE 34 Reverse disproportionation of an n-butane/n-heptane feed at100° C., 1700 rpm, Hastelloy C autoclave, wt. % of feed and reactionmixture time (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P Other^(a) C4P C5PiC4/nC4 iC5/nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.11 99.880.00 0.00 NA 0.0^(b) 0.0 0.0 90.2 0.0 0.0 0.0 9.8 0.0 0.0 90.1 0.0 0.0NA 0.2 0.63 13.31 73.09 4.25 0.64 1.82 5.37 0.39 0.50 86.40 4.89 0.186.64 4.6 2.66 41.61 37.75 10.33 2.70 3.36 0.76 0.44 0.39 79.36 13.031.10 3.83 ^(a)Other compounds present, ^(b)wt. % composition at t = 0 his based on mass of added reagents

Example 32 C3P/nC7—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 110°C.

A 300 mL Hastelloy B autoclave equipped with a Hastelloy B dipleg andHastelloy B nut and connector, Hastelloy B baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110°: oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.341 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with4.020 g of 2-chloro-2-methylpropane and 12.233 g of n-heptane, bothcompounds having previously been dried over activated 3A molecularsieves. The sample cylinder was closed under nitrogen, and both theautoclave and sample cylinder were removed from the glovebox. Theautoclave was charged with 86 g of propane from a pressurized feedcharger, displacing the nitrogen present in the autoclave. Thecomposition of the propane feed is listed in Table 35, entry 1. Theautoclave was heated to about 90° C. with stirring at about 700 rpm.Stirring was then stopped, and the 2-chloro-2-methylpropane/n-heptanesolution in the sample cylinder was added with an over-pressure ofnitrogen. The nitrogen used to pressurize the charger and for all otherwork passed over a separate high surface sodium column. Once theaddition was complete, stirring was set to 1700 rpm, and the mixture washeated to 110° C. It required 14 minutes to bring the mixture from theinitial temperature of 96° C. to 110° C. The pressure increased from 950psi (6.55 MPa) to 1460 psi (10.07 MPa) during this time. After 3.6 h,the temperature was decreased to 90° C., and the mixture was analyzed byonline and offline (GC. In order to analyze the paraffinic layer withonline GC, the stirring was stopped, and the product was allowed tosettle for 5 minutes. An aliquot was sampled directly from the autoclaveby opening a valve from the autoclave, passing the paraffinic layerthrough a SiO₂ column, and then passing it directly into a GC sampleloop. The GC method employed was UOP690. Afterwards, a liquid sample wasremoved by filtering through a SiO₂ column into a sample cylinder foroffline GC analysis. The liquid contained within the sample cylinder waspressurized with nitrogen to about 300 psi (2.07 MPa) and was thenanalyzed offline using an analogous method as described above. Thereported results are those from the offline analysis and are depicted inTable 7. The reaction mixture was then reheated to 110° C. which took1.7 h to stabilize at 110° C., and allowed to keep reacting. Thisprocedure was repeated one more time and the results are reported inTable 35. The mass ratio of liquid catalyst to hydrocarbon feed was0.43, and the volume ratio was 0.16 using the following densities: 1.34g/mL for the liquid catalyst, 0.684 g/mL for n-heptane and 0.49 g/mL forpropane.

TABLE 35 Reverse disproportionation of a propane/n-heptane feed at 110°C., 1700 rpm, Hastelloy B autoclave, wt. % of feed and reaction mixturetime (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P Other^(a) C4P C5P iC4/nC4iC5/nC5 NA 99.25 0.06 0.00 0.08 0.00 0.61 0.00 0.00 0.00 0.06 0.08 NA NA0.0^(b) 88.0 0.0 0.0 0.0 0.0 0.0 12.0 0.0 0.0 0.0 0.0 NA NA 3.6 86.806.07 2.30 2.44 0.64 1.16 0.46 0.04 0.09 8.37 3.08 2.64 3.81 21.4 85.597.27 3.85 1.84 0.52 0.69 0.10 0.00 0.14 11.12 2.36 1.89 3.54 ^(a)Othercompounds present, ^(b)wt. % composition at t = 0 h is based on mass ofadded reagents

Example 33 nC4/nC5—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy B autoclave equipped with a Hastelloy B dipleg andHastelloy B nut and connector, Hastelloy B baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.34 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with4.02 g of 2-chloro-2-methylpropane and 9.44 g of n-pentane, bothcompounds having previously been dried over activated 3A molecularsieves. The sample cylinder was closed under nitrogen, and both theautoclave and sample cylinder were removed from the glovebox. Theautoclave was charged with 43 g of n-butane from a pressurized feedcharger, without displacing the nitrogen present in the autoclave. Thecomposition of the n-butane feed is listed in Table 36, entry 1. Theautoclave was then charged with 92 g of n-pentane from a pressurizedfeed charger, which passed over a high surface sodium drier, withoutdisplacing the nitrogen. The autoclave was heated to 100° C. withstirring at 100 rpm. Once the temperature was achieved, stirring wasstopped, and the 2-chloro-2-methylpropane/n-pentane solution in thesample cylinder was added with an over-pressure of nitrogen. Thenitrogen used to pressurize the charger and for all other work passedover a separate high surface sodium column. Once the addition wascomplete, stirring was set to 1700 rpm. Initially, the temperatureincreased to 105° C., and the pressure was 1240 psi (8.55 MPa) withinthe autoclave. After 20 minutes of stirring, the temperature decreasedto 100° C., and the pressure was 1050 psi (7.24 MPa). After 20 minutes,stirring was stopped, and the paraffinic layer was analyzed by onlineand offline GC. In order to analyze the paraffinic layer with online GC,the stirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The GCmethod employed was UOP690. Afterwards, a liquid sample was removed byfiltering through a SiO₂ column into a sample cylinder for offline GCanalysis. The liquid contained within the sample cylinder waspressurized with nitrogen to about 300 psi (2.07 MPa) and was thenanalyzed offline using an analogous method as described above. Thereported results are those from the offline analysis and are depicted inTable 36. This procedure was repeated one more time and the results arereported in Table 36. The mass ratio of liquid catalyst to hydrocarbonfeed was 0.29, and the volume ratio was 0.13 using the followingdensities: 1.34 g/mL for the liquid catalyst, 0.626 g/mL for n-pentaneand 0.57 g/mL for n-butane.

TABLE 36 Disproportionation/reverse disproportionation of ann-butane/n-pentane feed at 100° C., 1700 rpm, Hastelloy B autoclave, wt.% of feed and reaction mixture time (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8POther^(a) C4P C5P iC4/nC4 iC5/nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.000.00 0.11 99.88 0.00 0.00 NA 0.0^(b) 0.0 0.0 30.0 0.0 70.0 0.0 0.0 0.00.0 30.0 70.0 0.00 NA 0.3 0.72 14.79 22.71 15.64 33.98 7.65 2.43 0.791.29 37.50 49.62 0.65 0.46 23.6 4.01 33.20 18.26 18.39 5.37 12.51 4.001.77 2.49 51.46 23.76 1.82 3.42 ^(a)Other compounds present, ^(b)wt. %composition at t = 0 h is based on mass of added reagents

Example 34 nC6 Isomerization and Disproportionation—Stir Rate at 1700rpm with [1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy B Autoclaveat 100° C.

A 300 mL Hastelloy B autoclave equipped with a Hastelloy B dipleg,Hastelloy B nut and connector and Hastelloy B baffle, and a 50 mLstainless steel sample cylinder were dried in a 110° C. oven for atleast 8 h. The dried autoclave and sample cylinder were then broughtinto a nitrogen glovebox. The autoclave was charged with 38.34 g of[1-butyl-3-methylimidazolium][Al₂Cl₇] and 129.4 g of n-hexane, which hadpreviously been dried over activated 3A molecular sieves, and theautoclave head was attached. The 50 mL sample cylinder was then chargedwith 4.02 g of 2-chloro-2-methylpropane, which had previously been driedover activated 3A molecular sieves, and 10.0 g of the n-hexane feed. Thesample cylinder was closed under nitrogen, and both the autoclave andthe sample cylinder were removed from the glovebox. The composition ofthe n-hexane feed is listed in Table 37, entry 1. The autoclave was thenheated to 100° C. with stirring at 300 rpm for 29 minutes, followed bystirring at 93 rpm for 30 minutes until the reaction temperature wasreached. At this point, stirring was stopped, and the2-chloro-2-methylpropane/n-hexane solution in the sample cylinder wasadded with an over-pressure of nitrogen. The nitrogen used to pressurizethe charger and for all other work passed over a separate high surfacesodium column. Once the addition was complete, stirring was set to 1700rpm. Initially, the temperature decreased to 96° C. after 6 minutes ofstirring, and the pressure was 340 psi (2.34 MPa) within the autoclave.After 6 minutes of reaction, the reaction mixture was analyzed by GC(entry 2. Table 37). During the course of the reaction, the reactionmixture was periodically analyzed online by GC. The pressure within theautoclave varied from 320-340 psi (2.21 to 2.34 MPa) at 100° C. duringthe course of the reaction. In order to analyze the paraffinic layer,the stirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The GCmethod employed was UOP690. The mass ratio of liquid catalyst tohydrocarbon feed was 0.30, and the volume ratio was 0.15 using thefollowing densities: 1.34 g % mL for the liquid catalyst and 0.659 g/mLfor n-hexane. The mass reaction rate was 760, and the volume reactionrate was 1500 after 0.1 h.

TABLE 37 Isomerization and disproportionation of n-hexane at 100° C.,1700 rpm, Hastelloy B autoclave, wt. % of feed and reaction mixture En-time nC4- nC5- nC6- nC7- nC8- nC9- try (h) C3P C4P C5P nC6 iC6 C7P C8PC7N C8N C8A nC5^(a) nC6^(a) nC7^(a) nC8^(a) nC9^(a) nC10^(a) nC10+^(a) 10.0 0.00 0.00 0.00 98.02 1.34 0.60 0.00 0.00 0.00 0.00 0.03 0.00 0.000.00 0.00 0.00 0.01 2 0.1 0.21 3.84 4.94 73.53 9.83 3.03 0.44 0.22 0.340.05 0.00 0.00 0.00 0.22 0.42 0.38 0.47 3 1.2 0.73 12.20 13.33 45.0814.92 6.62 1.63 0.57 0.80 0.09 0.02 0.00 0.00 0.00 1.32 1.12 1.55 4 4.00.80 13 26 14.58 38.16 15.80 7.95 2.22 0.62 1.08 0.12 0.00 0.00 0.020.00 1.79 1.48 2.07 ^(a)Unknowns eluting between the retention times forthese normal paraffins and ^(b)unknown eluting after nC10

Example 35 nC4/FT Wax—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy B autoclave equipped with a Hastelloy B dipleg andHastelloy B nut and connector, Hastelloy B baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.34 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with23.62 g of a commercially available FT wax. The sample cylinder wasclosed under nitrogen, and both the autoclave and sample cylinder wereremoved from the glovebox. The autoclave containing the ionic liquid wasthen put under vacuum (50 mTorr, 6.7 Pa) and 2 g of anhydrous HCl wascharged into the autoclave. The autoclave was then charged with 115 g ofn-butane from a pressurized feed charger, without displacing the gasespresent in the autoclave. The composition of the n-butane feed is listedin Table 38, entry 1. The sample cylinder containing the FT wax wascharged with 10.51 g of n-butane, and the cylinder was then heated to80° C. in an oven. The autoclave was heated to 100° C. with stirring at100 rpm. Once the temperature was achieved, stirring was stopped and theFT wax/n-butane solution in the sample cylinder was added with anover-pressure of nitrogen. Not all of the material was added: about29.39 g of the material was added based on the mass difference withinthe sample cylinder before and after addition. Assuming that thematerial added was of similar composition to what was initially presentin the sample cylinder, 20.3 g of FT wax and an additional 9.0 g ofn-butane were added. The nitrogen used to pressurize the charger and forall other work passed over a separate high surface sodium column. Oncethe addition was complete, stirring was set to 1700 rpm. Initially, thetemperature increased to 102° C., and the pressure was 760 psi (5.24MPa) within the autoclave. After 11 minutes of stirring, the temperaturestabilized at 100° C. and the pressure was 765 psi (5.27 MPa). After 3.3hours, stirring was stopped, and the paraffinic layer was analyzed byonline GC. In order to analyze the paraffinic layer with online GC, thestirring was stopped, and the product was allowed to settle for 5minutes. An aliquot was sampled directly from the autoclave by opening avalve from the autoclave, passing the paraffinic layer through a SiO₂column, and then passing it directly into a GC sample loop. The GCmethod employed was UOP690. The reported results are depicted in Table38. This procedure was repeated one more time and the results arereported in Table 38.

TABLE 38 Reverse disproportionation of an n-butane/FT wax feed at 100°C., 1700 rpm, Hastelloy B autoclave, wt. % of feed and reaction mixturetime (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC18+ Other^(a) C4P C5P iC4/nC4iC5/nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.00 0.11 99.88 0.000.00 NA 0.0^(b) 0.0 0.0 86 0.0 70.0 0.0 0.0 0.0 14 0 86 0.0 0.00 NA 3.33.33 39.29 26.20 15.74 4.38 7.62 1.67 1.09 0.05 0.63 65.49 20.12 1.503.59 19.5 8.08 35.52 20.16 16.94 4.78 10.20 2.24 1.18 0.15 0.75 55.6821.72 1.76 3.54 ^(a)Other compounds present, ^(b)wt. % composition at t= 0 h is based on mass of added reagents

Example 36 nC4/nC7—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy B autoclave equipped with a Hastelloy B dipleg andHastelloy B nut and connector, Hastelloy B baffle, and 75 mL stainlesssteel sample cylinder were dried in a 110° C. oven for at least 8 h. Thedried autoclave and sample cylinder were brought into a nitrogenglovebox and allowed to cool to ambient temperature. The autoclave wascharged with 38.34 g of [1-butyl-3-methylimidazolium][Al₂Cl₇], and theautoclave head was attached. The 75 mL sample cylinder was charged with43.30 g of n-heptane, which had previously been dried over activated 3Amolecular sieves. The sample cylinder was closed under nitrogen, andboth the autoclave and sample cylinder were removed from the glovebox.The autoclave containing the ionic liquid was then put under vacuum (100mTorr, 13.3 Pa) and 2 g of anhydrous HCl was charged into the autoclave.The autoclave was then charged with 85 g of n-butane from a pressurizedfeed charger, without displacing the gases present in the autoclave. Thecomposition of the n-butane feed is listed in Table 39, entry 1. Theautoclave was heated to 100° C. with stirring at 100 rpm. Once thetemperature was achieved stirring was stopped and the n-heptane solutionin the sample cylinder was added with an over-pressure of nitrogen,42.94 g was actually added. The nitrogen used to pressurize the chargerand for all other work passed over a separate high surface sodiumcolumn. Once the addition was complete, stirring was set to 1700 rpm.Initially, the temperature decreased to 96° C., and the pressure was 570psi (3.93 MPa) within the autoclave. After 7 minutes of stirring, thetemperature increased to 101° C. and the pressure was 540 psi (3.72MPa). After 7 minutes, stirring was stopped and the paraffinic layeranalyzed by online GC. In order to analyze the paraffinic layer withonline GC, the stirring was stopped, and the product was allowed tosettle for 5 minutes. An aliquot was sampled directly from the autoclaveby opening a valve from the autoclave, passing the paraffinic layerthrough a SiO₂ column, and then passing it directly into a GC sampleloop. The GC method employed was UOP690. After stirring was recommenced,the temperature stabilized at 100° C. after an additional 33 minutes ofreaction. The results are depicted in Table 39. This procedure wasrepeated two more times and the results are reported in Table 39. Themass ratio of liquid catalyst to hydrocarbon feed was 0.32, and thevolume ratio was 0.14 using the following densities: 1.34 g/mL for theliquid catalyst, 0.684 g/mL for n-heptane and 0.57 g/mL for n-butane.

TABLE 39 Disproportionation/reverse disproportionation of ann-butane/n-heptane feed at 100° C., 1700 rpm, Hastelloy B autoclave, wt.% of feed and reaction mixture time (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8POther^(a) C4P C5P iC4/nC4 iC5/nC5 NA 0.01 0.17 99.71 0.00 0.00 0.00 0.000.00 0.11 99.88 0.00 0.00 NA 0.0^(b) 0.0 0.0 66 0.0 70.0 0.0 34 0.0 0.066 0.0 0.00 NA 0.1 1.02 12.06 47.16 8.52 1.21 6.08 20.30 1.70 1.95 59.229.73 0.26 7.04 5 3.19 30.44 27.57 16.83 4.41 10.02 3.98 1.86 1.70 58.0121.24 1.10 3.82 21.5 4.91 34.56 21.19 17.66 4.97 10.63 2.98 1.61 1.4955.75 22.63 1.63 3.55 ^(a)Other compounds present, ^(b)wt. % compositionat t = 0 h is based on mass of added reagents

Example 37 nC4/nC5—Stir Rate at 1700 rpm with[1-butyl-3-methylimidazolium][Al₂Cl₇] in Hastelloy C Autoclave at 100°C.

A 300 mL Hastelloy B autoclave equipped with a Hastelloy B dipleg andHastelloy B nut and connector and a Hastelloy B baffle were dried in a110° C. oven for at least 8 h. The dried autoclave was brought into anitrogen glovebox and allowed to cool to ambient temperature. Theautoclave was charged with 38.34 g of[1-butyl-3-methylimidazolium][Al₂Cl₇], and the autoclave head wasattached. The autoclave was removed from the glovebox. The autoclavecontaining the ionic liquid was then put under vacuum (90 mTorr, 12.0Pa), and 2 g of anhydrous HCl was charged into the autoclave. Theautoclave was then charged with 41 g of n-butane from a pressurized feedcharger, without displacing the gases present in the autoclave. Thecomposition of the n-butane feed is listed in Table 40, entry 1. Theautoclave was next charged with 96 g of n-pentane, which passed over ahigh surface sodium drier, from a pressurized feed charger, the mixturewas stirred at ambient temperature for 5 minutes, and the reactionmixture was analyzed by online GC. In order to analyze the paraffiniclayer with online GC, the stirring was stopped, and the product wasallowed to settle for 5 minutes. An aliquot was sampled directly fromthe autoclave by opening a valve from the autoclave, passing theparaffinic layer through a SiO₂ column, and then passing it directlyinto a GC sample loop. The GC method employed was UOP690. After stirringwas recommenced, the mixture was heated to 100° C., which took 49minutes to reach. Once the temperature reached 100° C., the pressure was830 psi (5.72 MPa). After 27 minutes of reaction at 100° C., thepressure was 910 psi (6.27 MPa). At this point, the reaction mixture wasanalyzed by online GC using the procedure described above. The reactionwas continued at 100° C., and the results are depicted in Table 40. Themass ratio of liquid catalyst to hydrocarbon feed was 0.29, and thevolume ratio was 0.13 using the following densities: 1.34 g/mL for theliquid catalyst, 0.626 g/mL for n-pentane and 0.57 g/mL for n-butane.

TABLE 40 Disproportionation/reverse disproportionation of ann-butane/n-pentane feed at 100° C., 1700 rpm, Hastelloy B autoclave, wt.% of feed and reaction mixture time iC4/ iC5/ (h) C3P iC4 nC4 iC5 nC5C6P C7P C8P nC8+ Other^(a) C4P C5P nC4 nC5 NA 0.01 0.17 99.71 0.00 0.000.00 0.00 0.00 0.00 0.11 99.88 0.00 0.00 NA 0.0^(b) 0.0 0.29 23.49 0.9274.96 0.17 0.06 0.00 0.04 0.07 23.78 75.88 0.01 0.01 1.3 1.29 29.1119.18 19.77 7.87 13.58 4.83 2.23 1.64 0.50 48.29 27.64 1.52 2.51 6.33.09 32.05 18.27 19.37 5.57 13.75 4.18 2.05 1.33 0.34 50.32 24.94 1.753.48 24.3 5.34 31.64 17.77 18.60 5.34 13.86 3.90 1.92 1.31 0.32 49.4123.94 1.78 3.48 ^(a)Other compounds present, ^(b)wt. % composition forthe first GC recorded at ambient temperature

Example 38 Tuning Examples Using Above Data—C/H=0.41

The data shown in Table 41 are from Examples 33, 35 and 36 at the end ofthe run. As illustrated in these Examples, the feed C/H molar ratio issimilar, so the product composition should be similar at the end of thereaction if it is substantially equilibrated even though the startingfeed compositions are significantly different.

TABLE 41 1 2 3 Feed (wt. %) C3P 0.0 0.0 0.0 C4P 85.9 66.4 29.8 C5P 0.00.0 70.2 C6P 0.0 0.0 0.0 C7P 0.0 33.6 0.0 C8P 0.0 0.0 0.0 C9+ 14.1 (FTWax) 0.0 0.0 SUM 100.0 100.0 100.0 C/H 0.408^(a) 0.412 0.412 Product(wt. %) C3P 8.1 4.9 4.0 C4P 55.7 55.8 51.5 C5P 21.7 22.6 23.8 C6P 10.210.6 12.5 C7P 2.2 3.0 4.0 C8P 1.2 1.6 1.8 C9+ 0.3 0.7 1.8 SUM 99.4 99.299.3 % C4P Conversion 35 16 −72 % C9+ Conversion >99 NA NA % C7PConversion NA 91 NA % C5P Conversion NA NA 66 Wt. % Selectivity C3P 18 89 C4P 0 0 46 C5P 49 56 0 C6P 23 26 27 C7P 5 0 9 C8P 3 5 4 C9+ 1 2 4 SUM99 97 99 ^(a)Using the % C and % H values determined from analysis ofthe FT wax using the ASTM D5291 method

Example 39 Tuning Examples Using Above Data—C/H=0.40

The data shown in Table 42 are from Examples 18, 26 and 27 at the end ofthe run. As illustrated in these Examples, the feed C/H molar ratio issimilar, so the product composition should be similar at the end of thereaction if it is substantially equilibrated even though the startingfeed compositions are significantly different.

TABLE 42 1 2 3 Feed (wt. %) C3P 0.0 0.0 0.0 C4P 76.5 90.1 87.6 C5P 23.50.0 0.0 C6P 0.0 0.0 0.0 C7P 0.0 9.9 0.0 C8P 0.0 0.0 0.0 C9+ 0.0 0.0 12.4(nC9) SUM 100.0 100.0 100.0 C/H 0.404 0.403 0.406 Product (wt. %) C3P1.4 5.2 3.4 C4P 74.4 77.1 76.4 C5P 17.2 13.9 14.9 C6P 5.3 2.9 4.0 C7P0.7 0.4 0.6 C8P 0.6 0.2 0.3 C9+ 0.2 0.1 0.2 SUM 99.8 99.8 99.8 % C4PConversion 3 14% 13% % C5P Conversion 27 NA NA % C7P Conversion NA 96 NA% nC9 Conversion NA NA >99 Wt. % Selectivity C3P 16 23 14 C4P 0 0 0 C5P0 62 63 C6P 63 13 17 C7P 9 0 2 C8P 7 1 1 C9+ 3 0 1 SUM 98 99 98

While at least one exemplary embodiment has been presented in theforegoing detailed description of the invention, it should beappreciated that a vast number of variations exist. It should also beappreciated that the exemplary embodiment or exemplary embodiments areonly examples, and are not intended to limit the scope, applicability,or configuration of the invention in any way. Rather, the foregoingdetailed description will provide those skilled in the art with aconvenient road map for implementing an exemplary embodiment of theinvention. It being understood that various changes may be made in thefunction and arrangement of elements described in an exemplaryembodiment without departing from the scope of the invention as setforth in the appended claims.

What is claimed is:
 1. A process of tuning a hydrocarbon productcomposition comprising: selecting a range of paraffins; determining aseries of equilibrium constants for reactions of the selected range ofparaffins; selecting a desired product composition based on anequilibrium composition; selecting a hydrocarbon feed based on thedesired product composition, the selected hydrocarbon feed comprising atleast one C_(n) alkane where n=1-200: determining a feed ratio based onthe selected hydrocarbon feed and the desired product composition;reacting the selected hydrocarbon feed by contacting the selectedhydrocarbon feed with a liquid catalyst in the determined feed ratio ina reaction zone under tuning conditions to form the desired productcomposition, the liquid catalyst comprising an ionic liquid and acarbocation promoter; and recovering the desired product composition. 2.The process of claim 1 further comprising: selecting a C/H molar ratiowhich yields the desired product composition as determined from theseries of equilibrium constants; wherein selecting the desired productcomposition based on the equilibrium composition comprises selecting thedesired product composition based on the equilibrium composition at theselected C/H molar ratio; wherein determining the feed ratio based onthe selected hydrocarbon feed and the desired product compositioncomprises determining the feed ratio based on the selected hydrocarbonfeed, the desired product composition, and the selected C/H molar ratio.3. The process of claim 2 wherein the C/H molar ratio of the selectedhydrocarbon feed is in the range of about 0.25 to about 0.50.
 4. Theprocess of claim 1 further comprising: selecting a desired range of adesired property for the desired product composition, wherein thedesired property is at least one of research octane number, boilingpoint, boiling range, cloud point, pour point, viscosity, density andReid vapor pressure; and wherein selecting the hydrocarbon feed based onthe desired product composition comprises selecting the hydrocarbon feedbased on the desired product composition and the desired property. 5.The process of claim 1 wherein the ionic liquid comprises an organiccation and an anion and wherein the organic cation is selected from thegroup consisting of:

and lactamium based cations, where R¹-R²¹ are independently selectedfrom C₁-C₂₀ hydrocarbons, C₁-C₂₀ hydrocarbon derivatives, halogens, andH; and wherein the anion is derived from halides, sulfates, bisulfates,nitrates, sulfonates, fluoroalkanesulfonates, or combinations thereof.6. The process of claim 1 further comprising separating the ionic liquidfrom the product composition and regenerating the separated ionicliquid.
 7. The process of claim 1 wherein the tuning conditions compriseat least one of a temperature in a range of −20° C. to the decompositiontemperature of the ionic liquid, and a pressure in a range of about 0MPa to about 20.7 MPa.
 8. A process of tuning a hydrocarbon productcomposition comprising: selecting a range of paraffins; determining aseries of equilibrium constants for reactions of the selected range ofparaffins; determining an equilibrium composition of the selected rangeof paraffins as a function of C/H molar ratio; selecting a hydrocarbonfeed to react, the selected hydrocarbon feed comprising at least oneC_(n) alkane where n=1-200; and reacting the selected hydrocarbon feedby contacting the selected hydrocarbon feed with a liquid catalyst in areaction zone under tuning conditions to form the product composition,the liquid catalyst comprising an ionic liquid and a carbocationpromoter.
 9. The process of claim 8 wherein the C/H molar ratio of theselected hydrocarbon feed is in the range of about 0.25 to about 0.50.10. The process of claim 8 further comprising: selecting a desired rangeof a desired property for the product composition, wherein the desiredproperty is at least one of research octane number, boiling point,boiling range, cloud point, pour point, viscosity, density and Reidvapor pressure; and wherein selecting the hydrocarbon feed comprisesselecting the hydrocarbon feed based on the product composition and thedesired property.
 11. The process of claim 8 wherein the productcomposition comprises at least one C_(z) alkane where n<z<m, and whereinthe selected hydrocarbon feed comprises a first C_(n) alkane wheren=1-4, and a second C_(m) alkane where m=5-12.
 12. The process of claim8 wherein the product composition comprises at least one C_(z) alkanewhere n<z<m, and wherein the selected hydrocarbon feed comprises a firstC_(n) alkane where n=1-9, and a second C_(m) alkane where m=6-16. 13.The process of claim 8 wherein the product composition comprises atleast one C: alkane where n<z<m, and wherein the selected hydrocarbonfeed comprises a first C_(n) alkane where n=1-10, and a second C_(m)alkane where m=6-25.
 14. The process of claim 8 wherein the productcomposition comprises at least one C_(z) alkane where n<z<m, and whereinthe selected hydrocarbon feed comprises a first C_(n) alkane wheren=1-28, and a second C_(m) alkane where m=6-100.
 15. The process ofclaim 8 wherein the ionic liquid comprises an organic cation and ananion and wherein the organic cation is selected from the groupconsisting of:

and lactamium based cations, where R¹-R²¹ are independently selectedfrom C₁-C₂₀ hydrocarbons, C₁-C₂₀ hydrocarbon derivatives, halogens, andH; and wherein the anion is derived from halides, sulfates, bisulfates,nitrates, sulfonates, fluoroalkanesulfonates, or combinations thereof.16. The process of claim 8 wherein the carbocation promoter compriseshalo-alkanes, mineral acids, or combinations thereof and wherein a molarratio of the carbocation promoter to ionic liquid is in a range of about0:1 to about 3:1.
 17. The process of claim 8 further comprisingseparating the ionic liquid from the product composition andregenerating the separated ionic liquid.
 18. The process of claim 8wherein the tuning conditions comprise at least one of a temperature ina range of −20° C. to the decomposition temperature of the ionic liquid,and a pressure in a range of about 0 MPa to about 20.7 MPa.
 19. Theprocess of claim 8 further comprising: selecting a desired equilibriumproduct composition from the equilibrium composition corresponding to aselected C/H molar ratio; wherein the hydrocarbon feed is selected basedon the desired equilibrium product composition, and wherein the C/Hmolar ratio of the selected hydrocarbon feed matches the selected C/Hmolar ratio of the desired equilibrium product composition; wherein theselected hydrocarbon feed is reacted to form the desired substantiallyequilibrium product composition; and recovering the desiredsubstantially equilibrium product composition.
 20. The process of claim8 further comprising: determining the C/H molar ratio of the selectedhydrocarbon feed; determining the equilibrium composition at the C/Hmolar ratio for the selected hydrocarbon feed; wherein the selectedhydrocarbon feed is reacted to form a desired non-equilibrium productcomposition; and recovering the desired non-equilibrium productcomposition.